Bacterial attachment to RO membranes surface-modified by concentration-polarization-enhanced graft polymerization.

PubMed

Bernstein, Roy; Belfer, Sofia; Freger, Viatcheslav

2011-07-15

Concentration polarization-enhanced radical graft polymerization, a facile surface modification technique, was examined as an approach to reduce bacterial deposition onto RO membranes and thus contribute to mitigation of biofouling. For this purpose an RO membrane ESPA-1 was surface-grafted with a zwitterionic and negatively and positively charged monomers. The low monomer concentrations and low degrees of grafting employed in modifications moderately reduced flux (by 20-40%) and did not affect salt rejection, yet produced substantial changes in surface chemistry, charge and hydrophilicity. The propensity to bacterial attachment of original and modified membranes was assessed using bacterial deposition tests carried out in a parallel plate flow setup using a fluorescent strain of Pseudomonas fluorescens. Compared to unmodified ESPA-1 the deposition (mass transfer) coefficient was significantly increased for modification with the positively charged monomer. On the other hand, a substantial reduction in bacterial deposition rates was observed for membranes modified with zwitterionic monomer and, still more, with very hydrophilic negatively charged monomers. This trend is well explained by the effects of surface charge (as measured by ζ-potential) and hydrophilicity (contact angle). It also well correlated with force distance measurements by AFM using surrogate spherical probes with a negative surface charge mimicking the bacterial surface. The positively charged surface showed a strong hysteresis with a large adhesion force, which was weaker for unmodified ESPA-1 and still weaker for zwitterionic surface, while negatively charged surface showed a long-range repulsion and negligible hysteresis. These results demonstrate the potential of using the proposed surface- modification approach for varying surface characteristics, charge and hydrophilicity, and thus minimizing bacterial deposition and potentially reducing propensity biofouling.

On the physics of both surface overcharging and charge reversal at heterophase interfaces.

PubMed

Wang, Zhi-Yong; Zhang, Pengli; Ma, Zengwei

2018-02-07

The conventional paradigm for characterizing surface overcharging and charge reversal is based on the so-called Stern layer, in which surface dissociation reaction and specific chemical adsorption are assumed to take place. In this article, a series of Monte Carlo simulations have been applied to obtain useful insights into the underlying physics responsible for these two kinds of anomalous phenomena at the interface of two dielectrics, with special emphasis on the case of divalent counterions that are more relevant in natural and biological environments. At a weakly charged surface, it is found that independent of the type of surface charge distribution and the dielectric response of the solution, the overcharging event is universally driven by the ion size-asymmetric effect. Exceptionally, the overcharging still persists when the surface is highly charged but is only restricted to the case of discrete surface charge in a relatively low dielectric medium. As compared to the adsorption onto the homogeneously smeared charge surface that has the same average affinity for counterions, on the other hand, charge reversal under the action of a dielectric response can be substantially enhanced in the discrete surface charge representation due to strong association of counterions with interfacial groups, and the degree of enhancement depends in a nontrivial way on the reduction of the medium dielectric constant and the steric effects of finite ion size. Rather interestingly, the charge reversal is of high relevance to the overcharging of interfaces because the overwhelming interfacial association forces the coions closer to the surface due to their smaller size than the counterions. Upon the addition of a monovalent salt to the solution, the interfacial association with divalent counterions makes surface overcharging and charge reversal widely unaffected, in contrast to the prevailing notion that screening of surface charge of a homogeneous nature is determined by the competitive effects between size-exclusion effects and energetic contributions. Overall, the present work highlights that the complex interplay between the electrostatic and steric interactions should be coupled to the realistic character of surface charge to establish a faithful description of the overcharging and charge reversal at heterophase interfaces.

Effect of plasma-induced surface charging on catalytic processes: application to CO2 activation

NASA Astrophysics Data System (ADS)

Bal, Kristof M.; Huygh, Stijn; Bogaerts, Annemie; Neyts, Erik C.

2018-02-01

Understanding the nature and effect of the multitude of plasma-surface interactions in plasma catalysis is a crucial requirement for further process development and improvement. A particularly intriguing and rather unique property of a plasma-catalytic setup is the ability of the plasma to modify the electronic structure, and hence chemical properties, of the catalyst through charging, i.e. the absorption of excess electrons. In this work, we develop a quantum chemical model based on density functional theory to study excess negative surface charges in a heterogeneous catalyst exposed to a plasma. This method is specifically applied to investigate plasma-catalytic CO2 activation on supported M/Al2O3 (M = Ti, Ni, Cu) single atom catalysts. We find that (1) the presence of a negative surface charge dramatically improves the reductive power of the catalyst, strongly promoting the splitting of CO2 to CO and oxygen, and (2) the relative activity of the investigated transition metals is also changed upon charging, suggesting that controlled surface charging is a powerful additional parameter to tune catalyst activity and selectivity. These results strongly point to plasma-induced surface charging of the catalyst as an important factor contributing to the plasma-catalyst synergistic effects frequently reported for plasma catalysis.

Suppression of surface charge accumulation on Al{sub 2}O{sub 3}-filled epoxy resin insulator under dc voltage by direct fluorination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Boya; Zhang, Guixin, E-mail: guixin@mail.tsinghua.edu.cn; Li, Chuanyang

2015-12-15

Surface charge accumulation on insulators under high dc voltage is a major factor that may lead to the reduction of insulation levels in gas insulated devices. In this paper, disc insulators made of Al{sub 2}O{sub 3}-filled epoxy resin were surface fluorinated using a F{sub 2}/N{sub 2} mixture (12.5% F{sub 2}) at 50 °C and 0.1 MPa for different durations of 15 min, 30 min and 60 min. A dc voltage was applied to the insulator for 30 min and the charge density on its surface was measured by an electrostatic probe. The results revealed significant lower surface charge densities on themore » fluorinated insulators in comparison with the original one. Surface conductivity measurements indicated a higher surface conductivity by over three orders of magnitude after fluorination, which would allow the charges to transfer along the surface and thus may suppress their accumulation. Further, attenuated total reflection infrared analysis and surface morphology observations of the samples revealed that the introduction of fluoride groups altered the surface physicochemical properties. These structure changes, especially the physical defects reduced the depth of charge traps in the surface layer, which was verified by the measurement of energy distributions of the electron and hole traps based on the isothermal current theory. The results in this paper demonstrate that fluorination can be a promising and effective method to suppress surface charge accumulation on epoxy insulators in gas insulated devices.« less

Chemically rechargeable battery

NASA Technical Reports Server (NTRS)

Graf, James E. (Inventor); Rowlette, John J. (Inventor)

1984-01-01

Batteries (50) containing oxidized, discharged metal electrodes such as an iron-air battery are charged by removing and storing electrolyte in a reservoir (98), pumping fluid reductant such as formalin (aqueous formaldehyde) from a storage tank (106) into the battery in contact with the surfaces of the electrodes. After sufficient iron hydroxide has been reduced to iron, the spent reductant is drained, the electrodes rinsed with water from rinse tank (102) and then the electrolyte in the reservoir (106) is returned to the battery. The battery can be slowly electrically charged when in overnight storage but can be quickly charged in about 10 minutes by the chemical procedure of the invention.

Polymeric membranes: surface modification for minimizing (bio)colloidal fouling.

PubMed

Kochkodan, Victor; Johnson, Daniel J; Hilal, Nidal

2014-04-01

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London-van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized. Copyright © 2013 Elsevier B.V. All rights reserved.

Surface charge-induced EDL interaction on the contact angle of surface nanobubbles.

PubMed

Jing, Dalei; Li, Dayong; Pan, Yunlu; Bhushan, Bharat

2016-11-01

The contact angle (CA) of surface nanobubbles is believed to affect the stability of nanobubbles and fluid drag in micro/nanofluidic systems. The CA of nanobubbles is dependent on size and is believed to be affected by the surface charge-induced electrical double layer (EDL). However, neither of these of attributes are well understood. In this paper, by introducing an EDL-induced electrostatic wetting tension, a theoretical model is first established to study the effect of EDLs formed near the solid-liquid interface and the liquid-nanobubble interface on the gas phase CA of nanobubbles. The size-dependence of this EDL interaction is studied as well. Next, by using atomic force microscopy (AFM), the effect of the EDL on nanobubbles' gas phase CA is studied with variable electrical potential at the solid-liquid interface, which is adjusted by an applied voltage. Both the theoretical and the experimental results show that the EDLs formed near the solid-liquid interface and the liquid-nanobubble interface lead to a reduction of gas phase CA of the surface nanobubbles because of an electrostatic wetting tension on the nanobubble due to the attractive electrostatic interaction between the liquid and nanobubble within the EDL, which is in the nanobubbles' outward direction. An EDL with a larger zeta potential magnitude leads to a larger gas phase CA reduction. Furthermore, the effect of EDL on the nanobubbles' gas phase CA shows a significant size-dependence considering the size dependence of the electrostatic wetting tension. The gas phase CA reduction due to the EDL decreases with increasing nanobubble height and increases with the nanobubble's increasing curvature radius, indicating that a surface charge-induced EDL could possibly explain the size dependence of the gas phase CA of nanobubbles.

Carbon nanotubes decorated with Pt nanoparticles via electrostatic self-assembly: a highly active oxygen reduction electrocatalyst

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Sheng; Shao, Yuyan; Yin, Geping

2010-03-20

Carbon nanotubes (CNTs) are noncovalently functionalized with poly(allylamine hydrochloride) (PAH) and then employed as the support of Pt nanoparticles. X-Ray photoelectron spectroscopy confirms the successful functionalization of CNTs with PAH. The negatively charged Pt precursors are adsorbed on positively charged PAH-wrapping CNTs surface via electrostatic self-assembly and then in situ reduced in ethylene glycol. X-Ray diffraction and transmission electron microscope images reveal that Pt nanoparticles with an average size of 2.6 nm are uniformly dispersed on CNT surface. Pt/PAH-CNTs exhibit unexpectedly high activity towards oxygen reduction reaction, which can be attributed to the large electrochemical surface area of Pt nanoparticles.more » It also shows enhanced electrochemical stability due to the structural integrity of PAH-CNTs. This provides a facile approach to synthesize CNTs-based nanoelectrocatalysts.« less

Nanosecond pulsed electric field induced changes in cell surface charge density.

PubMed

Dutta, Diganta; Palmer, Xavier-Lewis; Asmar, Anthony; Stacey, Michael; Qian, Shizhi

2017-09-01

This study reports that the surface charge density changes in Jurkat cells with the application of single 60 nanosecond pulse electric fields, using atomic force microscopy. Using an atomic force microscope tip and Jurkat cells on silica in a 0.01M KCl ionic concentration, we were able to measure the interfacial forces, while also predicting surface charge densities of both Jurkat cell and silica surfaces. The most important finding is that the pulsing conditions varyingly reduced the cells' surface charge density. This offers a novel way in which to examine cellular effects of pulsed electric fields that may lead to the identification of unique mechanical responses. Compared to a single low field strength NsPEF (15kV/cm) application, exposure of Jurkat cells to a single high field strength NsPEF (60kV/cm) resulted in a further reduction in charge density and major morphological changes. The structural, physical, and chemical properties of biological cells immensely influence their electrostatic force; we were able to investigate this through the use of atomic force microscopy by measuring the surface forces between the AFM's tip and the Jurkat cells under different pulsing conditions as well as the interfacial forces in ionic concentrations. Copyright © 2017 Elsevier Ltd. All rights reserved.

The impact of nano-coating on surface charge accumulation of epoxy resin insulator: characteristic and mechanism

NASA Astrophysics Data System (ADS)

Qi, Bo; Gao, Chunjia; Lv, Yuzhen; Li, Chengrong; Tu, Youping; Xiong, Jun

2018-06-01

The flashover phenomenon of the insulator is the main cause for insulating failure of GIS/GIL, and one of the most critical impacting factors is the accumulation of surface charge. The common methods to restrain the surface charge accumulation are reviewed in this paper. Through the reasonable comparison and analysis of these methods, nano-coatings for the insulator were selected as a way to restrain the surface charge accumulation. Based on this, six nano-coated epoxy resin samples with different concentrations of P25-TiO2 nanoparticles were produced. A high precision 3D surface charge measurement system was developed in this paper with a spatial resolution of 4.0 mm2 and a charge resolution of 0.01 µC (m2 · mV)‑1. The experimental results for the epoxy resin sample showed that with the concentration of nanoparticles of the coating material increasing, the surface charge density tended to first decrease and then increase. In the sample coated with 0.5% concentration of nanoparticles, the suppression effect is the optimum, leading to a 63.8% reduction of charge density under DC voltage. The application test for actual nano-coated GIS/GIL basin insulator indicated that the maximum suppression degree for the charge density under DC voltage could reach 48.3%, while it could reach 22.2% for switching impulse voltage and 12.5% for AC context. The control mechanism of nano-coatings on charge accumulation was proposed based on the analysis for surface morphology features and traps characteristics; the shallow traps dominate in the migration of charges while the deep traps operate on the charge accumulation. With the concentration of nanoparticles in nano-coating material mounting up, the density of shallow traps continuously increases, while for deep traps, it first decreases and then increases. For the sample with 0.5% concentration of nanoparticles coated, the competition between shallow traps and deep traps comes to the most balanced state, producing the most significant suppression impact on surface charge accumulation.

Suppression of low-frequency charge noise in superconducting resonators by surface spin desorption.

PubMed

de Graaf, S E; Faoro, L; Burnett, J; Adamyan, A A; Tzalenchuk, A Ya; Kubatkin, S E; Lindström, T; Danilov, A V

2018-03-20

Noise and decoherence due to spurious two-level systems located at material interfaces are long-standing issues for solid-state quantum devices. Efforts to mitigate the effects of two-level systems have been hampered by a lack of knowledge about their chemical and physical nature. Here, by combining dielectric loss, frequency noise and on-chip electron spin resonance measurements in superconducting resonators, we demonstrate that desorption of surface spins is accompanied by an almost tenfold reduction in the charge-induced frequency noise in the resonators. These measurements provide experimental evidence that simultaneously reveals the chemical signatures of adsorbed magnetic moments and highlights their role in generating charge noise in solid-state quantum devices.

The motion of a charged particle on a Riemannian surface under a non-zero magnetic field

NASA Astrophysics Data System (ADS)

Castilho, Cesar Augusto Rodrigues

In this thesis we study the motion of a charged particle on a Riemmanian surface under the influence of a positive magnetic field B. Using Moser's Twist Theorem and ideas from classical pertubation theory we find sufficient conditions to perpetually trap the motion of a particle with a sufficient large charge in a neighborhood of a level set of the magnetic field. The conditions on the level set of the magnetic field that guarantee the trapping are local and hold near all non- degenerate critical local minima or maxima of B. Using sympletic reduction we apply the results of our work to certain S1-invariant magnetic fields on R3.

The Motion of a Charged Particle on a Riemannian Surface under a Non-Zero Magnetic Field

NASA Astrophysics Data System (ADS)

Castilho, César

2001-03-01

In this paper we study the motion of a charged particle on a Riemmanian surface under the influence of a positive magnetic field B. Using Moser's Twist Theorem and ideas from classical pertubation theory we find sufficient conditions to perpetually trap the motion of a particle with a sufficient large charge in a neighborhood of a level set of the magnetic field. The conditions on the level set of the magnetic field that guarantee the trapping are local and hold near all non-degenerate critical local minima or maxima of B. Using symplectic reduction we apply the results of our work to certain S1-invariant magnetic fields on R3.

Influence of natural organic matter on equilibrium adsorption of neutral and charged pharmaceuticals onto activated carbon.

PubMed

de Ridder, D J; Verliefde, A R D; Heijman, S G J; Verberk, J Q J C; Rietveld, L C; van der Aa, L T J; Amy, G L; van Dijk, J C

2011-01-01

Natural organic matter (NOM) can influence pharmaceutical adsorption onto granular activated carbon (GAC) by direct adsorption competition and pore blocking. However, in the literature there is limited information on which of these mechanisms is more important and how this is related to NOM and pharmaceutical properties. Adsorption batch experiments were carried out in ultrapure, waste- and surface water and fresh and NOM preloaded GAC was used. Twenty-one pharmaceuticals were selected with varying hydrophobicity and with neutral, negative or positive charge. The influence of NOM competition and pore blocking could not be separated. However, while reduction in surface area was similar for both preloaded GACs, up to 50% lower pharmaceutical removal was observed on wastewater preloaded GAC. This was attributed to higher hydrophobicity of wastewater NOM, indicating that NOM competition may influence pharmaceutical removal more than pore blocking. Preloaded GAC was negatively charged, which influenced removal of charged pharmaceuticals significantly. At a GAC dose of 6.7 mg/L, negatively charged pharmaceuticals were removed for 0-58%, while removal of positively charged pharmaceuticals was between 32-98%. Charge effects were more pronounced in ultrapure water, as it contained no ions to shield the surface charge. Solutes with higher log D could compete better with NOM, resulting in higher removal.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Taylor, S. D.; Becker, U.; Rosso, K. M.

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed,more » such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis for experimental interrogation of this important process at mineral-water interfaces.« less

Properties of an αs-casein-rich casein fraction: influence of dialysis on surface properties, miscibility, and micelle formation.

PubMed

Kessler, Anne; Menéndez-Aguirre, Orquidéa; Hinrichs, Jörg; Stubenrauch, Cosima; Weiss, Jochen

2013-09-01

In this study, the surface tension, miscibility, and particle size distribution of a solution containing an αs-casein (CN)-rich CN fraction (54 wt % αs-CN, 32 wt % β-CN, and 15 wt % κ-CN) were determined at pH 6.6. The nondialyzed CN fraction was compared with a dialyzed one. In the nondialyzed sample, every charge on the protein was compensated by 0.3 charges coming from counterions, whereas in the dialyzed sample, only 0.2 charges could be assigned to each charge on the protein. This relation was determined by calculating the charges at the proteins, taking the measured mineral content into account. The surface tension was measured as a function of the protein concentration by the du Noüy ring method at room temperature. Results indicated alterations in the surface properties after reduction of counterions. The equilibrium surface tension above the critical micelle concentration increased from 40.1×10(-3) to 45×10(-3) N/m, the critical micelle concentration increased from 0.9×10(-4) to 2×10(-3) mol/L, and the minimal area occupied per molecule at the surface increased from 2.4×10(-18) to 4.6×10(-18) m(2). Cloud points were determined by measuring the absorbance of CN solutions as a function of the temperature. The cloud points were found to be concentration dependent and had a minimum at 0.2 wt % at 34°C for nondialyzed CN and at 0.25 wt % at 28°C for dialyzed CN, again demonstrating the influence of counterion reduction. Below the cloud point, a micellar phase was found to exist. The hydrodynamic diameter of the micelles were characterized by dynamic light scattering in both auto- and cross-correlation mode. However, no influence of reduction in counterions could be observed, possibly due to the fact that dynamic light scattering is not a suitable method for this type of system. The presence of self-assembled structures was verified by freeze-fracture electron microscopy. The observed differences between dialyzed and nondialyzed samples were explained by changes in the counterion cloud surrounding the proteins. Consequently, the electrostatic interactions between as well as within the CN are altered by dialysis, which, in turn, affects the behavior at the surface as well as the properties in the solution. Copyright © 2013 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Fabrication of Poly(styrene-co-maleic anhydride)@Ag Spheres with High Surface Charge Intensity and their Self-Assembly into Photonic Crystal Films.

PubMed

Bi, Jiajie; Fan, Genrui; Wu, Suli; Su, Xin; Xia, Hongbo; Zhang, Shu-Fen

2017-10-01

Herein, we developed a method to prepare monodisperse poly(styrene-co-maleic anhydride)@Ag (PSMA@Ag) core-shell microspheres with high surface charge intensity by using an in situ reduction method. In this method, ethylenediamine tetraacetic acid tetrasodium salt (Na 4 EDTA) was used as a reducing agent to promote the growth of Ag, and at the same time endowed the PSMA@Ag spheres with a surface charge. The monodispersity of PSMA and PSMA@Ag and the ordered array of the photonic crystal films were characterized by using SEM. The formation of Ag nanoparticles was confirmed by using TEM, HR-TEM, and XRD characterizations. Due to the existence of surface charges, the obtained PSMA@Ag microspheres easily self-assembled to form photonic crystal structures. In addition, the surface-enhanced Raman scattering (SERS) activity of the PSMA@Ag photonic crystal films was evaluated by detecting the signal from Raman probe molecules, 4-aminothiophenol (4-ATP). The PSMA@Ag photonic crystal films exhibited a high SERS effect, a low detection limit of up to 10 -8 for 4-ATP, good uniformity, and reproducibility.

Enhanced biomimic bactericidal surfaces by coating with positively-charged ZIF nano-dagger arrays.

PubMed

Yuan, Yuan; Zhang, Yugen

2017-10-01

Cicada wing surfaces are covered with dense patterns of nano-pillar structure that prevent bacterial growth by rupturing adhered microbial cells. To mimic the natural nano-pillar structure, we developed a general and simple method to grow metal organic framework (MOF) nano-dagger arrays on a wide range of surfaces. These nano-daggers possess high bactericidal activity, with log reduction >7 for Escherichia coli and Staphylococcus aureus. It was hypothesized that the positively-charged ZIF-L nano-dagger surfaces enhance bacterial cell adhesion, facilitating selective and efficient bacteria killing by the rigid and sharp nano-dagger tips. This research provides a safe and clean antimicrobial surface technology which does not require external chemicals and will not cause drug resistance. Copyright © 2017 Elsevier Inc. All rights reserved.

Electro-osmotic flow in coated nanocapillaries: a theoretical investigation.

PubMed

Marini Bettolo Marconi, Umberto; Monteferrante, Michele; Melchionna, Simone

2014-12-14

Motivated by recent experiments, we present a theoretical investigation of how the electro-osmotic flow occurring in a capillary is modified when its charged surfaces are coated with charged polymers. The theoretical treatment is based on a three-dimensional model consisting of a ternary fluid-mixture, representing the solvent and two species for the ions, confined between two parallel charged plates decorated with a fixed array of scatterers representing the polymer coating. The electro-osmotic flow, generated by a constant electric field applied in a direction parallel to the plates, is studied numerically by means of Lattice Boltzmann simulations. In order to gain further understanding we performed a simple theoretical analysis by extending the Stokes-Smoluchowski equation to take into account the porosity induced by the polymers in the region adjacent to the walls. We discuss the nature of the velocity profiles by focusing on the competing effects of the polymer charges and the frictional forces they exert. We show evidence of the flow reduction and of the flow inversion phenomenon when the polymer charge is opposite to the surface charge. By using the density of polymers and the surface charge as control variables, we propose a phase diagram that discriminates the direct and the reversed flow regimes and determines their dependence on the ionic concentration.

Gypsum (CaSO4·2H2O) Scaling on Polybenzimidazole and Cellulose Acetate Hollow Fiber Membranes under Forward Osmosis

PubMed Central

Chen, Si Cong; Su, Jincai; Fu, Feng-Jiang; Mi, Baoxia; Chung, Tai-Shung

2013-01-01

We have examined the gypsum (CaSO4·2H2O) scaling phenomena on membranes with different physicochemical properties in forward osmosis (FO) processes. Three hollow fiber membranes made of (1) cellulose acetate (CA), (2) polybenzimidazole (PBI)/polyethersulfone (PES) and (3) PBI-polyhedral oligomeric silsesquioxane (POSS)/polyacrylonitrile (PAN) were studied. For the first time in FO processes, we have found that surface ionic interactions dominate gypsum scaling on the membrane surface. A 70% flux reduction was observed on negatively charged CA and PBI membrane surfaces, due to strong attractive forces. The PBI membrane surface also showed a slightly positive charge at a low pH value of 3 and exhibited a 30% flux reduction. The atomic force microscopy (AFM) force measurements confirmed a strong repulsive force between gypsum and PBI at a pH value of 3. The newly developed PBI-POSS/PAN membrane had ridge morphology and a contact angle of 51.42° ± 14.85° after the addition of hydrophilic POSS nanoparticles and 3 min thermal treatment at 95 °C. Minimal scaling and an only 1.3% flux reduction were observed at a pH value of 3. Such a ridge structure may reduce scaling by not providing a locally flat surface to the crystallite at a pH value of 3; thus, gypsum would be easily washed away from the surface. PMID:24957062

Mechanisms of Polyelectrolyte Enhanced Surfactant Adsorption at the Air-Water Interface

PubMed Central

Stenger, Patrick C.; Palazoglu, Omer A.; Zasadzinski, Joseph A.

2009-01-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids. PMID:19366599

Mechanisms of polyelectrolyte enhanced surfactant adsorption at the air-water interface.

PubMed

Stenger, Patrick C; Palazoglu, Omer A; Zasadzinski, Joseph A

2009-05-01

Chitosan, a naturally occurring cationic polyelectrolyte, restores the adsorption of the clinical lung surfactant Survanta to the air-water interface in the presence of albumin at much lower concentrations than uncharged polymers such as polyethylene glycol. This is consistent with the positively charged chitosan forming ion pairs with negative charges on the albumin and lung surfactant particles, reducing the net charge in the double-layer, and decreasing the electrostatic energy barrier to adsorption to the air-water interface. However, chitosan, like other polyelectrolytes, cannot perfectly match the charge distribution on the surfactant, which leads to patches of positive and negative charge at net neutrality. Increasing the chitosan concentration further leads to a reduction in the rate of surfactant adsorption consistent with an over-compensation of the negative charge on the surfactant and albumin surfaces, which creates a new repulsive electrostatic potential between the now cationic surfaces. This charge neutralization followed by charge inversion explains the window of polyelectrolyte concentration that enhances surfactant adsorption; the same physical mechanism is observed in flocculation and re-stabilization of anionic colloids by chitosan and in alternate layer deposition of anionic and cationic polyelectrolytes on charged colloids.

Engineering antiparallel charge-transfer cascades into supramolecular n/p-heterojunction photosystems: toward directional self-sorting on surfaces.

PubMed

Lista, Marco; Areephong, Jetsuda; Orentas, Edvinas; Charbonnaz, Pierre; Sakai, Naomi; Matile, Stefan

2012-01-01

This contribution describes recent progress made with the design, synthesis and evaluation of supramolecular architectures for artificial photosynthesis. Emphasis is on the possible introduction of antiparallel redox gradients into the co-axial hole- and electron-transporting channels of supramolecular n/p-heterojunctions, and on directional, uniform axial and alternate lateral self-sorting to get there. Recent results suggest that two-component gradients in both channels are sufficient for photoinduced charge separation over very long distances. Removal of one gradient leads to charge recombination at the usual critical distances, inversion of both gradients causes photocurrent inhibition. These promising results call for user-friendly, cheap and fast approaches to oriented multicomponent architectures on solid surfaces. However, the reduction of efforts devoted to covalent organic synthesis will have to be compensated by the development of strategic concepts on the supramolecular level to tackle basic questions such as self-sorting on surfaces.

Origin and evolution of surface spin current in topological insulators

NASA Astrophysics Data System (ADS)

Dankert, André; Bhaskar, Priyamvada; Khokhriakov, Dmitrii; Rodrigues, Isabel H.; Karpiak, Bogdan; Kamalakar, M. Venkata; Charpentier, Sophie; Garate, Ion; Dash, Saroj P.

2018-03-01

The Dirac surface states of topological insulators offer a unique possibility for creating spin polarized charge currents due to the spin-momentum locking. Here we demonstrate that the control over the bulk and surface contribution is crucial to maximize the charge-to-spin conversion efficiency. We observe an enhancement of the spin signal due to surface-dominated spin polarization while freezing out the bulk conductivity in semiconducting Bi1.5Sb0.5Te1.7Se1.3 below 100 K . Detailed measurements up to room temperature exhibit a strong reduction of the magnetoresistance signal between 2 and100 K , which we attribute to the thermal excitation of bulk carriers and to the electron-phonon coupling in the surface states. The presence and dominance of this effect up to room temperature is promising for spintronic science and technology.

Lattice Boltzmann Simulation of Electroosmotic Micromixing by Heterogeneous Surface Charge

NASA Astrophysics Data System (ADS)

Tang, G. H.; Wang, F. F.; Tao, W. Q.

Microelectroosmotic flow is usually restricted to low Reynolds number regime, and mixing in these microfluidic systems becomes problematic due to the negligible inertial effects. To gain an improved understanding of mixing enhancement in microchannels patterned with heterogeneous surface charge, the lattice Boltzmann method has been employed to obtain the electric potential distribution in the electrolyte, the flow field, and the species concentration distribution, respectively. The simulation results show that heterogeneous surfaces can significantly disturb the streamlines leading to apparently substantial improvements in mixing. However, the introduction of such a feature can reduce the mass flow rate in the channel. The reduction in flow rate effectively prolongs the available mixing time when the flow passes through the channel and the observed mixing enhancement by heterogeneous surfaces partly results from longer mixing time.

Double heterojunction nanowire photocatalysts for hydrogen generation

NASA Astrophysics Data System (ADS)

Tongying, P.; Vietmeyer, F.; Aleksiuk, D.; Ferraudi, G. J.; Krylova, G.; Kuno, M.

2014-03-01

Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities. Electronic supplementary information (ESI) available: Details of NW syntheses, processing and characterization. Additional TEM images of CdS, CdSe and CdSe/CdS core/shell NWs. NW concentration and cross section estimates. Details of the Pt NP decoration. Additional TEM images of Pt NP decorated CdS, CdSe and CdSe/CdS core/shell NWs. Size distribution of Pt NPs for CdSe/Pt NP and CdSe/CdS/Pt NP NWs. Xe arc lamp spectrum. Details of H2 generation experiments. Estimated photon absorption rate. Details of TDA measurements. TDA spectra and kinetics of CdS and CdS/Pt NP NWs. Plot illustrating CdSe NW band edge bleach kinetics. Comparison of CdSe band edge bleach kinetics in CdSe/CdS core/shell NWs when excited at λexc = 387 nm and λexc = 560 nm. Comparison of CdSe band edge bleach kinetics in CdSe/Pt NP NWs when excited at λexc = 387 nm and λexc = 560 nm. Bar graph showing H2 generation efficiencies of CdS and CdS/Pt NP NWs. Bleach kinetics of CdSe/CdS/Pt NP NWs at λexc = 387 nm and λexc = 560 nm. Comparison of CdS band edge bleach kinetics in CdS/Pt NP, and CdSe/CdS core/shell NWs when excited at λexc = 387 nm. See DOI: 10.1039/c4nr00298a

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Jing; Hu, Enyuan; Nordlund, Dennis

The phase transition, charge compensation, and local chemical environment of Ni in LiNiO 2 were investigated to understand the degradation mechanism. The electrode was subjected to a variety of bulk and surface-sensitive characterization techniques under different charge–discharge cycling conditions. We observed the phase transition from the original hexagonal H1 phase to another two hexagonal phases (H2 and H3) upon Li deintercalation. Moreover, the gradual loss of H3-phase features was revealed during the repeated charges. The reduction in Ni redox activity occurred at both the charge and the discharge states, and it appeared both in the bulk and at the surfacemore » over the extended cycles. In conclusion, the degradation of crystal structure significantly contributes to the reduction of Ni redox activity, which in turn causes the cycling performance decay of LiNiO 2.« less

Improvement of silicon solar cell efficiency by ion beam sputtered deposition of AlOxNy thin films.

PubMed

Chen, Sheng-Hui; Hsu, Chun-Che; Wang, Hsuan-Wen; Yeh, Chi-Li; Tseng, Shao-Ze; Lin, Hung-Ju; Lee, Cheng-Chung; Peng, Cheng-Yu

2011-03-20

Negative charge material, AlOxNy, has been fabricated to passivate the surface of p-type silicon. The fabrication of AlOxNy was possible by using ion beam sputtering deposition to deposit AlN thin film on the surface of a p-type silicon wafer and following annealing in oxygen ambient. Capacitance-voltage analysis shows the fixed charge density has increased from 10(11) cm(-2) to 2.26×10(12) cm(-2) after annealing. The solar cell efficiency increased from 15.9% to 17.3%, which is also equivalent to the reduction of surface recombination velocity from 1×10(5)  to 32 cm/s.

Effect of calcination temperature on the photocatalytic reduction and oxidation processes of hydrothermally synthesized titania nanotubes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Viayan, B.; Dimitrijevic, N. M.; Rajh, T.

Titania nanotubes having diameters 8 to 12 nm and lengths of 50-300 nm were prepared using a hydrothermal method. Further, the titania nanotubes were calcined over the temperature range 200-800 C in order to enhance their photocatalytic properties by altering their morphology. The calcined titania nanotubes were characterized by using X-ray diffraction and surface area analysis and their morphological features were studied by scanning and transmission electron microscopy. Nanotubes calcined at 400 C showed the maximum extent of photocatalyitc reduction of carbon dioxide to methane, whereas samples calcined at 600 C produced maximum photocatalytic oxidation of acetaldehyde. Electron paramagnetic resonancemore » (EPR) spectroscopy was used to interrogate the effects of nanotube structure on the charge separation and trapping as a function of calcination temperature. EPR results indicated that undercoordinated titania sites are associated with maximum CO{sub 2} reduction occurring in nanotubes calcined at 400 C. Despite the collapse of the nantube structure to form nanorods and the concomitant loss of surface area, the enhanced charge separation associated with increased crystallinity promoted high rates of oxidation of acetaldehyde in titania materials calcined at 600 C. These results illustrate that calcination temperature allows us to tune the morphological and surface features of the titania nanostructures for particular photocatalytic reactions.« less

PRE- AND POST-SYNAPTIC EFFECTS OF MANIPULATING SURFACE CHARGE WITH DIVALENT CATIONS AT THE PHOTORECEPTOR SYNAPSE

PubMed Central

CADETTI, L.; THORESON, W. B.; PICCOLINO, M.

2006-01-01

Persistence of horizontal cell (HC) light responses in extracellular solutions containing low Ca2+ plus divalent cations to block Ca2+ currents (ICa) has been attributed to Ca2+-independent neurotransmission. Using a retinal slice preparation to record both ICa and light responses, we demonstrate that persistence of HC responses in low [Ca2+]o can instead be explained by a paradoxical increase of Ca2+ influx into photoreceptor terminals arising from surface charge-mediated shifts in ICa activation. Consistent with this explanation, application of Zn2+ or Ni2+ caused a hyperpolarizing block of HC light responses that was relieved by lowering [Ca2+]o. The same concentrations of Zn2+ and Ni2+ reduced the amplitude of ICa at the rod dark potential and this reduction was relieved by a hyperpolarizing shift in voltage dependence induced by lowering [Ca2+]o. Block of ICa by Mg2+, which has weak surface charge effects, was not relieved by low [Ca2+]o. Recovery of HC responses in low [Ca2+]o was assisted by enhancement of rod light responses. To bypass light stimulation, OFF bipolar cells were stimulated by steps to −40 mV applied to presynaptic rods during simultaneous paired recordings. Consistent with surface charge theory, the post-synaptic current was inhibited by Zn2+ and this inhibition was relieved by lowering [Ca2+]o. Nominally divalent-free media produced inversion of HC light responses even though rod light responses remained hyperpolarizing; HC response inversion can be explained by surface charge-mediated shifts in ICa. In summary, HC light responses modifications induced by low divalent cation solutions can be explained by effects on photoreceptor light responses and membrane surface charge without necessitating Ca2+-independent neurotransmission. Furthermore, these results suggest that surface charge effects accompanying physiological changing divalent cation levels in the synaptic cleft may provide a means for modulating synaptic output from photoreceptors. PMID:15541900

Hexavalent chromium removal by chitosan modified-bioreduced nontronite

NASA Astrophysics Data System (ADS)

Singh, Rajesh; Dong, Hailiang; Zeng, Qiang; Zhang, Li; Rengasamy, Karthikeyan

2017-08-01

Recent efforts have focused on structural Fe(II) in chemically or biologically reduced clay minerals to immobilize Cr(VI) from aqueous solution, but the coulombic repulsion between the negatively charged clay surface and the polyanionic form of Cr(VI), e.g., dichromate, can hinder the effectiveness of this process. The purpose of this study was to investigate the efficiency and mechanism of Cr(VI) removal by a charge-reversed nontronite (NAu-2), an Fe-rich smectite. Chitosan, a linear polysaccharide derived from chitin found in soil and groundwater, was used to reverse the charge of NAu-2. Intercalation of chitosan into NAu-2 interlayer increased the basal d-spacing of NAu-2 from 1.23 nm to 1.83 nm and zeta potential from -27.17 to +34.13 mV, with the amount of increase depending on chitosan/NAu-2 ratio. Structural Fe(III) in chitosan-exchanged NAu-2 was then biologically reduced by an iron-reducing bacterium Shewanella putrefaciens CN32 in bicarbonate buffer with lactate as the sole electron donor, with and without electron shuttle, AQDS. Without AQDS, the extent of Fe(III) reduction increased from the lowest (∼9%) for the chitosan-free NAu-2 to the highest (∼12%) for the highest chitosan loaded NAu-2 (3:1 ratio). This enhancement of Fe(III) reduction was likely due to the attachment of negatively charged bacterial cells to charge-reversed (e.g., positively charged) NAu-2 surfaces, facilitating the electron transfer between cells and structural Fe(III). With AQDS, Fe(III) reduction extent doubled relative to those without AQDS, but the enhancement effect was similar across all chitosan loadings, suggesting that AQDS was more important than chitosan in enhancing Fe(III) bioreduction. Chitosan-exchanged, biologically reduced NAu-2 was then utilized for removing Cr(VI) in batch experiments with three consecutive spikes of 50 μM Cr. With the first Cr spike, the rate of Cr(VI) removal by charged-reversed NAu-2 that was bioreduced without and with AQDS was ∼1.5 and ∼6 μmol g-1 h-1, respectively. However, the capacity of these clays to remove Cr(VI) was progressively exhausted upon addition of subsequent Cr spikes. X-ray photoelectron spectroscopy (XPS) revealed that the reduction product of Cr(VI) by chitosan-exchanged-bioreduced NAu-2 was Cr(III), possibly in the form of Cr(OH)3. In summary, our results demonstrated that the combined effects of sorption and redox reactions by charge-reversed bioreduced nontronite may offer a feasible in-situ approach for remediating Cr(VI) polluted soil and groundwater.

Dual gas-diffusion membrane- and mediatorless dihydrogen/air-breathing biofuel cell operating at room temperature

NASA Astrophysics Data System (ADS)

Xia, Hong-qi; So, Keisei; Kitazumi, Yuki; Shirai, Osamu; Nishikawa, Koji; Higuchi, Yoshiki; Kano, Kenji

2016-12-01

A membraneless direct electron transfer (DET)-type dihydrogen (H2)/air-breathing biofuel cell without any mediator was constructed wherein bilirubin oxidase from Myrothecium verrucaria (BOD) and membrane-bound [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F (MBH) were used as biocatalysts for the cathode and the anode, respectively, and Ketjen black-modified water proof carbon paper (KB/WPCC) was used as an electrode material. The KB/WPCC surface was modified with 2-aminobenzoic acid and p-phenylenediamine, respectively, to face the positively charged electron-accepting site of BOD and the negatively charged electron-donating site of MBH to the electrode surface. A gas-diffusion system was employed for the electrodes to realize high-speed substrate supply. As result, great improvement in the current density of O2 reduction with BOD and H2 reduction with MBH were realized at negatively and postively charged surfaces, respectively. Gas diffusion system also suppressed the oxidative inactivation of MBH at high electrode potentials. Finally, based on the improved bioanode and biocathode, a dual gas-diffusion membrane- and mediatorless H2/air-breathing biofuel cell was constructed. The maximum power density reached 6.1 mW cm-2 (at 0.72 V), and the open circuit voltage was 1.12 V using 1 atm of H2 gas as a fuel at room temperature and under passive and quiescent conditions.

A Nonmetal Plasmonic Z-Scheme Photocatalyst with UV- to NIR-Driven Photocatalytic Protons Reduction.

PubMed

Zhang, Zhenyi; Huang, Jindou; Fang, Yurui; Zhang, Mingyi; Liu, Kuichao; Dong, Bin

2017-05-01

Ultrabroad-spectrum absorption and highly efficient generation of available charge carriers are two essential requirements for promising semiconductor-based photocatalysts, towards achieving the ultimate goal of solar-to-fuel conversion. Here, a fascinating nonmetal plasmonic Z-scheme photocatalyst with the W 18 O 49 /g-C 3 N 4 heterostructure is reported, which can effectively harvest photon energies spanning from the UV to the nearinfrared region and simultaneously possesses improved charge-carrier dynamics to boost the generation of long-lived active electrons for the photocatalytic reduction of protons into H 2 . By combining with theoretical simulations, a unique synergistic photocatalysis effect between the semiconductive Z-scheme charge-carrier separation and metal-like localized-surface-plasmon-resonance-induced "hot electrons" injection process is demonstrated within this binary heterostructure. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Understanding the Degradation Mechanism of Lithium Nickel Oxide Cathodes for Li-Ion Batteries

DOE PAGES

Xu, Jing; Hu, Enyuan; Nordlund, Dennis; ...

2016-11-01

The phase transition, charge compensation, and local chemical environment of Ni in LiNiO 2 were investigated to understand the degradation mechanism. The electrode was subjected to a variety of bulk and surface-sensitive characterization techniques under different charge–discharge cycling conditions. We observed the phase transition from the original hexagonal H1 phase to another two hexagonal phases (H2 and H3) upon Li deintercalation. Moreover, the gradual loss of H3-phase features was revealed during the repeated charges. The reduction in Ni redox activity occurred at both the charge and the discharge states, and it appeared both in the bulk and at the surfacemore » over the extended cycles. In conclusion, the degradation of crystal structure significantly contributes to the reduction of Ni redox activity, which in turn causes the cycling performance decay of LiNiO 2.« less

Identification of an Extracellular Polysaccharide Network Essential for Cytochrome Anchoring and Biofilm Formation in Geobacter sulfurreducens▿ †

PubMed Central

Rollefson, Janet B.; Stephen, Camille S.; Tien, Ming; Bond, Daniel R.

2011-01-01

Transposon insertions in Geobacter sulfurreducens GSU1501, part of an ATP-dependent exporter within an operon of polysaccharide biosynthesis genes, were previously shown to eliminate insoluble Fe(III) reduction and use of an electrode as an electron acceptor. Replacement of GSU1501 with a kanamycin resistance cassette produced a similarly defective mutant, which could be partially complemented by expression of GSU1500 to GSU1505 in trans. The Δ1501 mutant demonstrated limited cell-cell agglutination, enhanced attachment to negatively charged surfaces, and poor attachment to positively charged poly-d-lysine- or Fe(III)-coated surfaces. Wild-type and mutant cells attached to graphite electrodes, but when electrodes were poised at an oxidizing potential inducing a positive surface charge (+0.24 V versus the standard hydrogen electrode [SHE]), Δ1501 mutant cells detached. Scanning electron microscopy revealed fibrils surrounding wild-type G. sulfurreducens which were absent from the Δ1501 mutant. Similar amounts of type IV pili and pilus-associated cytochromes were detected on both cell types, but shearing released a stable matrix of c-type cytochromes and other proteins bound to polysaccharides. The matrix from the mutant contained 60% less sugar and was nearly devoid of c-type cytochromes such as OmcZ. The addition of wild-type extracellular matrix to Δ1501 cultures restored agglutination and Fe(III) reduction. The polysaccharide binding dye Congo red preferentially bound wild-type cells and extracellular matrix material over mutant cells, and Congo red inhibited agglutination and Fe(III) reduction by wild-type cells. These results demonstrate a crucial role for the xap (extracellular anchoring polysaccharide) locus in metal oxide attachment, cell-cell agglutination, and localization of essential cytochromes beyond the Geobacter outer membrane. PMID:21169487

Using supramolecular binding motifs to provide precise control over the ratio and distribution of species in multiple component films grafted on surfaces: demonstration using electrochemical assembly from aryl diazonium salts.

PubMed

Gui, Alicia L; Yau, Hon Man; Thomas, Donald S; Chockalingam, Muthukumar; Harper, Jason B; Gooding, J Justin

2013-04-16

Supramolecular interactions between two surface modification species are explored to control the ratio and distribution of these species on the resultant surface. A binary mixture of aryl diazonium salts bearing oppositely charged para-substituents (either -SO3(-) or -N(+)(Me)3), which also reduce at different potentials, has been examined on glassy carbon surfaces using cyclic voltammetry and X-ray photoelectron spectroscopy (XPS). Striking features were observed: (1) the two aryl diazonium salts in the mixed solution undergo reductive adsorption at the same potential which is distinctively less negative than the potential required for the reduction of either of the two aryl diazonium salts alone; (2) the surface ratio of the two phenyl derivatives is consistently 1:1 regardless of the ratio of the two aryl diazonium salts in the modification solutions. Homogeneous distribution of the two oppositely charged phenyl species on the modified surface has also been suggested by XPS survey spectra. Diffusion coefficient measurements by DOSY NMR and DFT based computation have indicated the association of the two aryl diazonium species in the solution, which has led to changes in the molecular orbital energies of the two species. This study highlights the potential of using intermolecular interactions to control the assembly of multicomponent thin layers.

Surface degradation of Li1-xNi0.80Co0.15Al0.05O2 cathodes: Correlating charge transfer impedance with surface phase transformations

NASA Astrophysics Data System (ADS)

Sallis, S.; Pereira, N.; Mukherjee, P.; Quackenbush, N. F.; Faenza, N.; Schlueter, C.; Lee, T.-L.; Yang, W. L.; Cosandey, F.; Amatucci, G. G.; Piper, L. F. J.

2016-06-01

The pronounced capacity fade in Ni-rich layered oxide lithium ion battery cathodes observed when cycling above 4.1 V (versus Li/Li+) is associated with a rise in impedance, which is thought to be due to either bulk structural fatigue or surface reactions with the electrolyte (or combination of both). Here, we examine the surface reactions at electrochemically stressed Li1-xNi0.8Co0.15Al0.05O2 binder-free powder electrodes with a combination of electrochemical impedance spectroscopy, spatially resolving electron microscopy, and spatially averaging X-ray spectroscopy techniques. We circumvent issues associated with cycling by holding our electrodes at high states of charge (4.1 V, 4.5 V, and 4.75 V) for extended periods and correlate charge-transfer impedance rises observed at high voltages with surface modifications retained in the discharged state (2.7 V). The surface modifications involve significant cation migration (and disorder) along with Ni and Co reduction, and can occur even in the absence of significant Li2CO3 and LiF. These data provide evidence that surface oxygen loss at the highest levels of Li+ extraction is driving the rise in impedance.

Detailed modeling of electron emission for transpiration cooling of hypersonic vehicles

NASA Astrophysics Data System (ADS)

Hanquist, Kyle M.; Hara, Kentaro; Boyd, Iain D.

2017-02-01

Electron transpiration cooling (ETC) is a recently proposed approach to manage the high heating loads experienced at the sharp leading edges of hypersonic vehicles. Computational fluid dynamics (CFD) can be used to investigate the feasibility of ETC in a hypersonic environment. A modeling approach is presented for ETC, which includes developing the boundary conditions for electron emission from the surface, accounting for the space-charge limit effects of the near-wall plasma sheath. The space-charge limit models are assessed using 1D direct-kinetic plasma sheath simulations, taking into account the thermionically emitted electrons from the surface. The simulations agree well with the space-charge limit theory proposed by Takamura et al. for emitted electrons with a finite temperature, especially at low values of wall bias, which validates the use of the theoretical model for the hypersonic CFD code. The CFD code with the analytical sheath models is then used for a test case typical of a leading edge radius in a hypersonic flight environment. The CFD results show that ETC can lower the surface temperature of sharp leading edges of hypersonic vehicles, especially at higher velocities, due to the increase in ionized species enabling higher electron heat extraction from the surface. The CFD results also show that space-charge limit effects can limit the ETC reduction of surface temperatures, in comparison to thermionic emission assuming no effects of the electric field within the sheath.

Nanotribological Properties of Positively and Negatively charged nanodiamonds as additives to solutions

NASA Astrophysics Data System (ADS)

Liu, Zijian; Corley, Steven; Shenderova, Olga; Brenner, Donald; Krim, Jacqueline

2013-03-01

Nano-diamond (ND) particles are known to be beneficial for wear and friction reduction when used as additives in liquids, but the fundamental origins of the improvement in tribological properties has not been established. In order to explore this issue, we have investigated the nanotribological properties of ND coated with self-assembled monolayers (SAM) as additives to solutions, employing gold/chrome coated quartz crystal microbalances (QCM). Measurements were performed with the QCM initially immersed in deionized water. ND particles with positively and negatively charged SAM end groups were then added to the water, while the frequency and amplitude of the QCM were monitored. Negative shifts in both the QCM frequency and amplitude were observed when ND with positively charged SAM end groups were added, while positive shifts in both the QCM frequency and amplitude were observed when ND with negatively charged ND end groups were added. The results are consistent with a lubricating effect for the negatively charged ND, but were only observed for sufficiently small negative ND particle size. Experiments on QCM surfaces with differing textures and roughness are in progress, to determine the separate contributing effects of surface roughness charge-water interactions. Funding provided by NSF DMR.

Long term stability of c-Si surface passivation using corona charged SiO2

NASA Astrophysics Data System (ADS)

Bonilla, Ruy S.; Reichel, Christian; Hermle, Martin; Hamer, Phillip; Wilshaw, Peter R.

2017-08-01

Recombination at the semiconductor surface continues to be a major limit to optoelectronic device performance, in particular for solar cells. Passivation films reduce surface recombination by a combination of chemical and electric field effect components. Dielectric films used for this purpose, however, must also accomplish optical functions at the cell surface. In this paper, corona charge is seen as a potential method to enhance the passivation properties of a dielectric film while maintaining its optical characteristics. It is observed that corona charge can produce extreme reductions in surface recombination via field effect, in the best case leading to lifetimes exceeding 5 ms at an injection of 1015 cm-3. For a 200 μm n-type 1 Ω cm c-Si wafer, this equates to surface recombination velocities below 0.65 cm/s and J0e values of 0.92 fA/cm2. The average improvement in passivation after corona charging gave lifetimes of 1-3 ms. This was stabilised for a period of 3 years by chemically treating the films to prevent water absorption. Surface recombination was kept below 7 cm/s, and J0e < 16.28 fA/cm2 for 3 years, with a decay time constant of 8.7 years. Simulations of back-contacted n-type cells show that front surface recombination represents less than 2% of the total internally generated power in the cell (the loss in power output) when the passivation is kept better than 16 fA/cm2, and as high as 10% if front recombination is worse than 100 fA/cm2.

Effects of adhesions of amorphous Fe and Al hydroxides on surface charge and adsorption of K+ and Cd2+ on rice roots.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Zhou, Qin; Xu, Ren-Kou

2017-11-01

Iron (Fe) and aluminum (Al) hydroxides in variable charge soils attached to rice roots may affect surface-charge properties and subsequently the adsorption and uptake of nutrients and toxic metals by the roots. Adhesion of amorphous Fe and Al hydroxides onto rice roots and their effects on zeta potential of roots and adsorption of potassium (K + ) and cadmium (Cd 2+ ) by roots were investigated. Rice roots adsorbed more Al hydroxide than Fe hydroxide because of the greater positive charge on Al hydroxide. Adhesion of Fe and Al hydroxides decreased the negative charge on rice roots, and a greater effect of the Al hydroxide. Consequently, adhesion of Fe and Al hydroxides reduced the K + and Cd 2+ adsorption by rice roots. The results of attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and desorption of K + and Cd 2+ from rice roots indicated that physical masking by Fe and Al hydroxides and diffuse-layer overlapping between the positively-charged hydroxides and negatively-charged roots were responsible for the reduction of negative charge on roots induced by adhesion of the hydroxides. Therefore, the interaction between Fe and Al hydroxides and rice roots reduced negative charge on roots and thus inhibited their adsorption of nutrient and toxic cations. Copyright © 2017 Elsevier Inc. All rights reserved.

Helium Ion Microscopy (HIM) for the imaging of biological samples at sub-nanometer resolution

NASA Astrophysics Data System (ADS)

Joens, Matthew S.; Huynh, Chuong; Kasuboski, James M.; Ferranti, David; Sigal, Yury J.; Zeitvogel, Fabian; Obst, Martin; Burkhardt, Claus J.; Curran, Kevin P.; Chalasani, Sreekanth H.; Stern, Lewis A.; Goetze, Bernhard; Fitzpatrick, James A. J.

2013-12-01

Scanning Electron Microscopy (SEM) has long been the standard in imaging the sub-micrometer surface ultrastructure of both hard and soft materials. In the case of biological samples, it has provided great insights into their physical architecture. However, three of the fundamental challenges in the SEM imaging of soft materials are that of limited imaging resolution at high magnification, charging caused by the insulating properties of most biological samples and the loss of subtle surface features by heavy metal coating. These challenges have recently been overcome with the development of the Helium Ion Microscope (HIM), which boasts advances in charge reduction, minimized sample damage, high surface contrast without the need for metal coating, increased depth of field, and 5 angstrom imaging resolution. We demonstrate the advantages of HIM for imaging biological surfaces as well as compare and contrast the effects of sample preparation techniques and their consequences on sub-nanometer ultrastructure.

Helium Ion Microscopy (HIM) for the imaging of biological samples at sub-nanometer resolution.

PubMed

Joens, Matthew S; Huynh, Chuong; Kasuboski, James M; Ferranti, David; Sigal, Yury J; Zeitvogel, Fabian; Obst, Martin; Burkhardt, Claus J; Curran, Kevin P; Chalasani, Sreekanth H; Stern, Lewis A; Goetze, Bernhard; Fitzpatrick, James A J

2013-12-17

Scanning Electron Microscopy (SEM) has long been the standard in imaging the sub-micrometer surface ultrastructure of both hard and soft materials. In the case of biological samples, it has provided great insights into their physical architecture. However, three of the fundamental challenges in the SEM imaging of soft materials are that of limited imaging resolution at high magnification, charging caused by the insulating properties of most biological samples and the loss of subtle surface features by heavy metal coating. These challenges have recently been overcome with the development of the Helium Ion Microscope (HIM), which boasts advances in charge reduction, minimized sample damage, high surface contrast without the need for metal coating, increased depth of field, and 5 angstrom imaging resolution. We demonstrate the advantages of HIM for imaging biological surfaces as well as compare and contrast the effects of sample preparation techniques and their consequences on sub-nanometer ultrastructure.

Role of electrostatic interactions in the toxicity of titanium dioxide nanoparticles toward Escherichia coli.

PubMed

Pagnout, Christophe; Jomini, Stéphane; Dadhwal, Mandeep; Caillet, Céline; Thomas, Fabien; Bauda, Pascale

2012-04-01

The increasing production and use of titanium dioxide nanoparticles (NP-TiO(2)) has led to concerns about their possible impact on the environment. Bacteria play crucial roles in ecosystem processes and may be subject to the toxicity of these nanoparticles. In this study, we showed that at low ionic strength, the cell viability of Escherichia coli was more severely affected at pH 5.5 than at pH 7.0 and pH 9.5. At pH 5.5, nanoparticles (positively charged) strongly interacted with the bacterial cells (negatively charged) and accumulated on their surfaces. This phenomenon was observed in a much lower degree at pH 7.0 (NP-TiO(2) neutrally charged and cells negatively charged) and pH 9.5 (both NP-TiO(2) and cells negatively charged). It was also shown that the addition of electrolytes (NaCl, CaCl(2), Na(2)SO(4)) resulted in a gradual reduction of the NP-TiO(2) toxicity at pH 5.5 and an increase in this toxicity at pH 9.5, which was closely related to the reduction of the NP-TiO(2) and bacterial cell electrostatic charges. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Automatic charge control system for satellites

NASA Technical Reports Server (NTRS)

Shuman, B. M.; Cohen, H. A.

1985-01-01

The SCATHA and the ATS-5 and 6 spacecraft provided insights to the problem of spacecraft charging at geosychronous altitudes. Reduction of the levels of both absolute and differential charging was indicated, by the emission of low energy neutral plasma. It is appropriate to complete the transition from experimental results to the development of a system that will sense the state-of-charge of a spacecraft, and, when a predetermined threshold is reached, will respond automatically to reduce it. A development program was initiated utilizing sensors comparable to the proton electrostatic analyzer, the surface potential monitor, and the transient pulse monitor that flew in SCATHA, and combine these outputs through a microprocessor controller to operate a rapid-start, low energy plasma source.

Conference Proceedings of Applied Computational Electromagnetics (2nd) Held at Monterey, California on 18-20 March 1986

DTIC Science & Technology

1986-03-01

only accurate to 10 percent when it began to diverge . This illustrates one of the caveats for using the BMI technique : convergence is not guaranteed...for a surface equates the divergence of surface current density at a point to the time rate of reduction of surface charge density. If a large scale...field at the point of reflection resolved into the components which permit the use of the reflection dyad, R. A(s) is the divergence coefficient which

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

PubMed

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

2017-06-27

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

PubMed Central

Favaro, Marco; Yano, Junko; Crumlin, Ethan J.

2017-01-01

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. PMID:28607092

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ˜550 °C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M2,3VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 °C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fazleev, N. G.; Department of Physics, Kazan State University, Kazan 420008; Nadesalingam, M. P.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The PAES intensity then decreases monotonically as the annealing temperature is increased to {approx}550 deg. C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M{sub 2,3}VV and O KLL Auger transitions. PAESmore » results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 deg. C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.« less

Charge transfer and symmetry reduction at the CuPc/Ag(110) interface studied by photoemission tomography

NASA Astrophysics Data System (ADS)

Schönauer, K.; Weiss, S.; Feyer, V.; Lüftner, D.; Stadtmüller, B.; Schwarz, D.; Sueyoshi, T.; Kumpf, C.; Puschnig, P.; Ramsey, M. G.; Tautz, F. S.; Soubatch, S.

2016-11-01

On the Ag(110) surface copper phthalocyanine (CuPc) orders in two structurally similar superstructures, as revealed by low-energy electron diffraction. Scanning tunneling microscopy (STM) shows that in both superstructures the molecular planes are oriented parallel to the surface and the long molecular axes, defined as diagonals of the square molecule, are rotated by ≃±32∘ away from the high-symmetry directions [1 1 ¯0 ] and [001] of the silver surface. Similarly to many other adsorbed metal phthalocyanines, the CuPc molecules on Ag(110) appear in STM as crosslike features with twofold symmetry. Photoemission tomography based on angle-resolved photoemission spectroscopy reveals a charge transfer from the substrate into the molecule. A symmetry analysis of experimental and theoretical constant binding energy maps of the photoemission intensity in the kx,ky -plane points to a preferential occupation of one of the two initially degenerate lowest unoccupied molecular orbitals (LUMOs) of eg symmetry. The occupied eg orbital is rotated by 32∘ against the [001] direction of the substrate. The lifting of the degeneracy of the LUMOs and the related reduction of the symmetry of the adsorbed CuPc molecule are attributed to an anisotropy in the chemical reactivity of the Ag(110) surface.

Using magnetic charge to understand soft-magnetic materials

NASA Astrophysics Data System (ADS)

Arrott, Anthony S.; Templeton, Terry L.

2018-04-01

This is an overview of what the Landau-Lifshitz-Gilbert equations are doing in soft-magnetic materials with dimensions large compared to the exchange length. The surface magnetic charges try to cancel applied magnetic fields inside the soft magnetic material. The exchange energy tries to reach a minimum while meeting the boundary conditions set by the magnetic charges by using magnetization patterns that have a curl but no divergence. It can almost do this, but it still pays to add some divergence to further lower the exchange energy. There are then both positively and negatively charged regions in the bulk. The unlike charges attract one another, but do not annihilate because they are paid for by the reduction in exchange energy. The micromagnetics of soft magnetic materials is about how those charges rearrange themselves. The topology of magnetic charge distributions presents challenges for mathematicians. No one guessed that they like to form helical patterns of extended multiples of charge density.

Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles.

PubMed

Dong, Hong; Snyder, James F; Tran, Dat T; Leadore, Julia L

2013-06-20

In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images. Copyright © 2013 Elsevier Ltd. All rights reserved.

New pathway to prepare gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering.

PubMed

Chang, Chun-Chao; Yang, Kuang-Hsuan; Liu, Yu-Chuan; Hsu, Ting-Chu

2012-05-01

As shown in the literature, additional energies are necessary for the reduction of positively charged noble metal ions to prepare metal nanoparticles (NPs). In this work, we report a new green pathway to prepare Au NPs in neutral 0.1M NaCl aqueous solutions from bulk Au substrates without addition of any stabilizer and reductant just via aid of natural chitosan (Ch) at room temperature. Au- and Ch-containing complexes in aqueous solution were electrochemically prepared. The role of Ch is just an intermediate to perform electron transfer with Au NPs. The stability of these prepared Au NPs is well maintained by Au NPs themselves with slightly positively charged Au remained on the surface of Au NPs. The particle size of prepared spherical Au (111) NPs is ca. 15 nm in diameter. Moreover, increasing the pH of preparation solutions can be contributive to preparing concentrated Au NPs in solutions. The prepared Au NPs are surface-enhanced Raman scattering (SERS)-active for probe molecules of Rhodamine 6G. They also demonstrate significantly catalytic activity for decomposition of acetaldehyde in rice wine. Copyright © 2012 Elsevier B.V. All rights reserved.

Underestimated role of the secondary electron emission in the space

NASA Astrophysics Data System (ADS)

Nemecek, Zdenek; Richterova, Ivana; Safrankova, Jana; Pavlu, Jiri; Vaverka, Jakub; Nouzak, Libor

2016-07-01

Secondary electron emission (SEE) is one of many processes that charges surfaces of bodies immersed into a plasma. Until present, a majority of considerations in theories and experiments is based on the sixty year old description of an interaction of planar metallic surfaces with electrons, thus the effects of a surface curvature, roughness, presence of clusters as well as an influence of the material conductance on different aspects of this interaction are neglected. Dust grains or their clusters can be frequently found in many space environments - interstellar clouds, atmospheres of planets, tails of comets or planetary rings are only typical examples. The grains are exposed to electrons of different energies and they can acquire positive or negative charge during this interaction. We review the progress in experimental investigations and computer simulations of the SEE from samples relevant to space that was achieved in course of the last decade. We present a systematic study of well-defined systems that starts from spherical grains of various diameters and materials, and it continues with clusters consisting of different numbers of small spherical grains that can be considered as examples of real irregularly shaped space grains. The charges acquired by investigated objects as well as their secondary emission yields are calculated using the SEE model. We show that (1) the charge and surface potential of clusters exposed to the electron beam are influenced by the number of grains and by their geometry within a particular cluster, (2) the model results are in an excellent agreement with the experiment, and (3) there is a large difference between charging of a cluster levitating in the free space and that attached to a planar surface. The calculation provides a reduction of the secondary electron emission yield of the surface covered by dust clusters by a factor up to 1.5 with respect to the yield of a smooth surface. (4) These results are applied on charging of the lunar surface and the dust grains levitating above it, and it is shown that the SEE is more important for isolated dust grains than for the lunar surface covered by them.

Effect of phosphorylation of myelin basic protein by MAPK on its interactions with actin and actin binding to a lipid membrane in vitro.

PubMed

Boggs, Joan M; Rangaraj, Godha; Gao, Wen; Heng, Yew-Meng

2006-01-17

Myelin basic protein (MBP) binds to negatively charged lipids on the cytosolic surface of oligodendrocyte membranes and is most likely responsible for adhesion of these surfaces in the multilayered myelin sheath. It can also polymerize actin, bundle F-actin filaments, and bind actin filaments to lipid bilayers through electrostatic interactions. MBP consists of a number of posttranslationally modified isomers of varying charge, some resulting from phosphorylation at several sites by different kinases, including mitogen-activated protein kinase (MAPK). Phosphorylation of MBP in oligodendrocytes occurs in response to various extracellular stimuli. Phosphorylation/dephosphorylation of MBP also occurs in the myelin sheath in response to electrical activity in the brain. Here we investigate the effect of phosphorylation of MBP on its interaction with actin in vitro by phosphorylating the most highly charged unmodified isomer, C1, at two sites with MAPK. Phosphorylation decreased the ability of MBP to polymerize actin and to bundle actin filaments but had no effect on the dissociation constant of the MBP-actin complex or on the ability of Ca2+-calmodulin to dissociate the complex. The most significant effect of phosphorylation on the MBP-actin complex was a dramatic reduction in its ability to bind to negatively charged lipid bilayers. The effect was much greater than that reported earlier for another charge isomer of MBP, C8, in which six arginines were deiminated to citrulline, resulting in a reduction of net positive charge of 6. These results indicate that although average electrostatic forces are the primary determinant of the interaction of MBP with actin, phosphorylation may have an additional effect due to a site-specific electrostatic effect or to a conformational change. Thus, phosphorylation of MBP, which occurs in response to various extracellular signals in both myelin and oligodendrocytes, attenuates the ability of MBP to polymerize and bundle actin and to bind it to a negatively charged membrane.

Charge of the containerless experimentation in microgravity

NASA Technical Reports Server (NTRS)

Lee, Mark C.

1990-01-01

The experimentation was undertaken to study the elimination or reduction of surface contamination for which there is adequate Earth-based technology along with the reduction of dynamic nucleation for which there a paucity of reliable data. One objective is to delineate scientific justification of the U.S. Containerless Experimentation Program in Microgravity for the next decade and beyond. Another objective is for the guidance of NASA to define the next generation of containerless experimentation instruments in microgravity.

Repulsion-based model for contact angle saturation in electrowetting

PubMed Central

2015-01-01

We introduce a new model for contact angle saturation phenomenon in electrowetting on dielectric systems. This new model attributes contact angle saturation to repulsion between trapped charges on the cap and base surfaces of the droplet in the vicinity of the three-phase contact line, which prevents these surfaces from converging during contact angle reduction. This repulsion-based saturation is similar to repulsion between charges accumulated on the surfaces of conducting droplets which causes the well known Coulombic fission and Taylor cone formation phenomena. In our model, both the droplet and dielectric coating were treated as lossy dielectric media (i.e., having finite electrical conductivities and permittivities) contrary to the more common assumption of a perfectly conducting droplet and perfectly insulating dielectric. We used theoretical analysis and numerical simulations to find actual charge distribution on droplet surface, calculate repulsion energy, and minimize energy of the total system as a function of droplet contact angle. Resulting saturation curves were in good agreement with previously reported experimental results. We used this proposed model to predict effect of changing liquid properties, such as electrical conductivity, and system parameters, such as thickness of the dielectric layer, on the saturation angle, which also matched experimental results. PMID:25759748

Repulsion-based model for contact angle saturation in electrowetting.

PubMed

Ali, Hassan Abdelmoumen Abdellah; Mohamed, Hany Ahmed; Abdelgawad, Mohamed

2015-01-01

We introduce a new model for contact angle saturation phenomenon in electrowetting on dielectric systems. This new model attributes contact angle saturation to repulsion between trapped charges on the cap and base surfaces of the droplet in the vicinity of the three-phase contact line, which prevents these surfaces from converging during contact angle reduction. This repulsion-based saturation is similar to repulsion between charges accumulated on the surfaces of conducting droplets which causes the well known Coulombic fission and Taylor cone formation phenomena. In our model, both the droplet and dielectric coating were treated as lossy dielectric media (i.e., having finite electrical conductivities and permittivities) contrary to the more common assumption of a perfectly conducting droplet and perfectly insulating dielectric. We used theoretical analysis and numerical simulations to find actual charge distribution on droplet surface, calculate repulsion energy, and minimize energy of the total system as a function of droplet contact angle. Resulting saturation curves were in good agreement with previously reported experimental results. We used this proposed model to predict effect of changing liquid properties, such as electrical conductivity, and system parameters, such as thickness of the dielectric layer, on the saturation angle, which also matched experimental results.

Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

PubMed

Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

2017-08-09

Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

Effects of polymer graft properties on protein adsorption and transport in ion exchange chromatography: a multiscale modeling study.

PubMed

Basconi, Joseph E; Carta, Giorgio; Shirts, Michael R

2015-04-14

Multiscale simulation is used to study the adsorption of lysozyme onto ion exchangers obtained by grafting charged polymers into a porous matrix, in systems with various polymer properties and strengths of electrostatic interaction. Molecular dynamics simulations show that protein partitioning into the polymer-filled pore space increases with the overall charge content of the polymers, while the diffusivity in the pore space decreases. However, the combination of greatly increased partitioning and modestly decreased diffusion results in macroscopic transport rates that increase as a function of charge content, as the large concentration driving force due to enhanced pore space partitioning outweighs the reduction in the pore space diffusivity. Matrices having greater charge associated with the grafted polymers also exhibit more diffuse intraparticle concentration profiles during transient adsorption. In systems with a high charge content per polymer and a low protein loading, the polymers preferentially partition toward the surface due to favorable interactions with the surface-bound protein. These results demonstrate the potential of multiscale modeling to illuminate qualitative trends between molecular properties and the adsorption equilibria and kinetic properties observable on macroscopic scales.

On gel electrophoresis of dielectric charged particles with hydrophobic surface: A combined theoretical and numerical study.

PubMed

Majee, Partha Sarathi; Bhattacharyya, Somnath; Gopmandal, Partha Pratim; Ohshima, Hiroyuki

2018-03-01

A theoretical study on the gel electrophoresis of a charged particle incorporating the effects of dielectric polarization and surface hydrophobicity at the particle-liquid interface is made. A simplified model based on the weak applied field and low charge density assumption is also presented and compared with the full numerical model for a nonpolarizable particle to elucidate the nonlinear effects such as double layer polarization and relaxation as well as surface conduction. The main motivation of this study is to analyze the electrophoresis of the surface functionalized nanoparticle with tunable hydrophobicity or charged fluid drop in gel medium by considering the electrokinetic effects and hydrodynamic interactions between the particle and the gel medium. An effective medium approach, in which the transport in the electrolyte-saturated hydrogel medium is governed by the Brinkman equation, is adopted in the present analysis. The governing electrokinetic equations based on the conservation principles are solved numerically. The Navier-slip boundary condition along with the continuity condition of dielectric displacement are imposed on the surface of the hydrophobic polarizable particle. The impact of the slip length on the electrophoresis is profound for a thinner Debye layer, however, surface conduction effect also becomes significant for a hydrophobic particle. Impact of hydrophobicity and relaxation effects are higher for a larger particle. Dielectric polarization creates a reduction in its electrophoretic propulsion and has negligible impact at the thinner Debye length as well as lower gel screening length. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

SPM observation of slow highly charged ion induced nanodots on highly orientated pyrolytic graphite

NASA Astrophysics Data System (ADS)

Mitsuda, Y.; Nakamura, B. E. O'Rourke1 N.; Kanai, Y.; Ohtani, S.; Yamazaki, Y.

2007-03-01

We have observed nanodots on a highly orientated pyrolytic graphite (HOPG) surface produced by highly charged ion impacts using a scanning tunneling microscope. Previous measurements have con.rmed the dominant role of the potential energy or the incident ion charge state on the size and height of the observed nanodots. The present results extend these previous measurements to much lower kinetic energy. It appears that there is no observable influence on the lateral size of the nanodots due to the incident ion kinetic energy down to approximately 200 eV. In contrast some slight reduction in the nanodot height was observed as the kinetic energy was reduced.

Hexahedron Prism-Anchored Octahedronal CeO2: Crystal Facet-Based Homojunction Promoting Efficient Solar Fuel Synthesis.

PubMed

Li, Ping; Zhou, Yong; Zhao, Zongyan; Xu, Qinfeng; Wang, Xiaoyong; Xiao, Min; Zou, Zhigang

2015-08-05

An unprecedented, crystal facet-based CeO2 homojunction consisting of hexahedron prism-anchored octahedron with exposed prism surface of {100} facets and octahedron surface of {111} facets was fabricated through solution-based crystallographic-oriented epitaxial growth. The photocatalysis experiment reveals that growth of the prism arm on octahedron allows to activate inert CeO2 octahedron for an increase in phototocatalytic reduction of CO2 into methane. The pronounced photocatalytic performance is attributed to a synergistic effect of the following three factors: (1) band alignment of the {100} and {111} drives electrons and holes to octahedron and prism surfaces, respectively, aiming to reach the most stable energy configuration and leading to a spatial charge separation for long duration; (2) crystallographic-oriented epitaxial growth of the CeO2 hexahedron prism arm on the octahedron verified by the interfacial lattice fringe provides convenient and fast channels for the photogenerated carrier transportation between two units of homojuntion; (3) different effective mass of electrons and holes on {100} and {111} faces leads to high charge carrier mobility, more facilitating the charge separation. The proposed facet-based homojunction in this work may provide a new concept for the efficient separation and fast transfer of photoinduced charge carriers and enhancement of the photocatalytic performance.

Using the electrochemical dimension to build water/Ru(0001) phase diagram

NASA Astrophysics Data System (ADS)

Lespes, Nicolas; Filhol, Jean-Sébastien

2015-01-01

The water monolayer/Ru(0001) electrochemical phase diagram as a function of surface potential and temperature is built using a DFT approach. The monolayer structure with temperature is extracted following the zero-charge line in good agreement with experiments. Below 140 K, a mix of oppositely charged hydroxyl/water and hydride/water domains is found stable; above 140 K, water molecules desorb from the hydride phase leading to a mixture of oppositely charged surface hydride and hydroxyl/water phases; above 280 K, all the residual adsorbed water desorbs. For undissociated water, a Chain structure is found stable and desorbs above 150 K. The observed nano-sized domains are suggested to be the balance between hydroxyl/hydride repulsion that tends to create two well separated domains and opposite charging that tends to favor a domain mix. An isotopic effect is computed to reduce by a factor of 160 the kinetic rate of D2O dissociation (compared to H2O) and is linked to the reduction of the ZPE in the transition state caused by a proton transport chain. Water monolayer/Ru(0001) has a specific reactivity and its organization is highly sensitive to the surface potential suggesting that under electrochemical conditions, the potential is not only tuning directly the chemical reactivity but also indirectly through the solvent structure.

Electrostatics of polymer translocation events in electrolyte solutions.

PubMed

Buyukdagli, Sahin; Ala-Nissila, T

2016-07-07

We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ≈10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.

Chitosan based atorvastatin nanocrystals: effect of cationic charge on particle size, formulation stability, and in-vivo efficacy

PubMed Central

Kurakula, Mallesh; El-Helw, AM; Sobahi, Tariq R; Abdelaal, Magdy Y

2015-01-01

Cationic charged chitosan as stabilizer was evaluated in preparation of nanocrystals using probe sonication method. The influence of cationic charge densities of chitosan (low CSL, medium CSM, high CSH molecular weights) and Labrasol® in solubility enhancement and modifying the release was investigated, using atorvastatin (ATR) as poorly soluble model drug. Compared to CSM and CSH; low cationic charge of CSL acted as both electrostatic and steric stabilizer by significant size reduction to 394 nm with charge of 21.5 meV. Solubility of ATR-CSL increased to 60-fold relative to pure ATR and ATR-L. Nanocrystals were characterized for physiochemical properties. Scanning electron microscopy revealed scaffold-like structures with high surface area. X-ray powder diffractometry and differential scanning calorimetry revealed crystalline to slight amorphous state changes after cationic charge size reduction. Fourier transform-infrared spectra indicated no potent drug-excipient interactions. The enhanced dissolution profile of ATR-CSL indicates that sustained release was achieved compared with ATR-L and Lipitor®. Anti-hyperlipidemic performance was pH dependent where ATR-CSL exhibited 2.5-fold higher efficacy at pH 5 compared to pH 6 and Lipitor®. Stability studies indicated marked changes in size and charge for ATR-L compared to ATR-CSL exemplifying importance of the stabilizer. Therefore, nanocrystals developed with CSL as a stabilizer is a promising choice to enhance dissolution, stability, and in-vivo efficacy of major Biopharmaceutical Classification System II/IV drugs. PMID:25609947

Mesoporous gold sponges: electric charge-assisted seed mediated synthesis and application as surface-enhanced Raman scattering substrates

NASA Astrophysics Data System (ADS)

Yi, Zao; Luo, Jiangshan; Tan, Xiulan; Yi, Yong; Yao, Weitang; Kang, Xiaoli; Ye, Xin; Zhu, Wenkun; Duan, Tao; Yi, Yougen; Tang, Yongjian

2015-11-01

Mesoporous gold sponges were prepared using 4-dimethylaminopyridine (DMAP)-stabilized Au seeds. This is a general process, which involves a simple template-free method, room temperature reduction of HAuCl4·4H2O with hydroxylamine. The formation process of mesoporous gold sponges could be accounted for the electrostatic interaction (the small Au nanoparticles (~3 nm) and the positively charged DMAP-stabilized Au seeds) and Ostwald ripening process. The mesoporous gold sponges had appeared to undergo electrostatic adsorption initially, sequentially linear aggregation, welding and Ostwald ripening, then, they randomly cross link into self-supporting, three-dimensional networks with time. The mesoporous gold sponges exhibit higher surface area than the literature. In addition, application of the spongelike networks as an active material for surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol (4-ATP) molecules as a probe.

Hα line shape in front of the limiter in the HT-6M tokamak

NASA Astrophysics Data System (ADS)

Wan, Baonian; Li, Jiangang; Luo, Jiarong; Xie, Jikang; Wu, Zhenwei; Zhang, Xianmei; HT-6M Group

1999-11-01

The Hα line shape in front of the limiter in the HT-6M tokamak is analysed by multi-Gaussian fitting. The energy distribution of neutral hydrogen atoms reveals that Hα radiation is contributed by Franck-Condon atoms, atoms reflected at the limiter surface and charge exchange. Multi-Gaussian fitting of the Hα spectral profile indicates contributions of 60% from reflection particles and 40% from molecule dissociation to recycling. Ion temperatures in central regions are obtained from the spectral width of charge exchange components. Dissociation of hydrogen molecules and reflection of particles at the limiter surface are dominant in edge recycling. Reduction of particle reflection at the limiter surface is important for controlling edge recycling. The measured profiles of neutral hydrogen atom density are reproduced by a particle continuity equation and a simplified one dimensional Monte Carlo simulation code.

Mesoporous gold sponges: electric charge-assisted seed mediated synthesis and application as surface-enhanced Raman scattering substrates

PubMed Central

Yi, Zao; Luo, Jiangshan; Tan, Xiulan; Yi, Yong; Yao, Weitang; Kang, Xiaoli; Ye, Xin; Zhu, Wenkun; Duan, Tao; Yi, Yougen; Tang, Yongjian

2015-01-01

Mesoporous gold sponges were prepared using 4-dimethylaminopyridine (DMAP)-stabilized Au seeds. This is a general process, which involves a simple template-free method, room temperature reduction of HAuCl4·4H2O with hydroxylamine. The formation process of mesoporous gold sponges could be accounted for the electrostatic interaction (the small Au nanoparticles (~3 nm) and the positively charged DMAP-stabilized Au seeds) and Ostwald ripening process. The mesoporous gold sponges had appeared to undergo electrostatic adsorption initially, sequentially linear aggregation, welding and Ostwald ripening, then, they randomly cross link into self-supporting, three-dimensional networks with time. The mesoporous gold sponges exhibit higher surface area than the literature. In addition, application of the spongelike networks as an active material for surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol (4-ATP) molecules as a probe. PMID:26538365

Impurity concentrations and surface charge densities on the heavily doped face of a silicon solar cell

NASA Technical Reports Server (NTRS)

Weinberg, I.; Hsu, L. C.

1977-01-01

Increased solar cell efficiencies are attained by reduction of surface recombination and variation of impurity concentration profiles at the n(+) surface of silicon solar cells. Diagnostic techniques are employed to evaluate the effects of specific materials preparation methodologies on surface and near surface concentrations. It is demonstrated that the MOS C-V method, when combined with a bulk measurement technique, yields more complete concentration data than are obtainable by either method alone. Specifically, new solar cell MOS C-V measurements are combined with bulk concentrations obtained by a successive layer removal technique utilizing measurements of sheet resistivity and Hall coefficient.

Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

NASA Astrophysics Data System (ADS)

Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

2014-03-01

Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

Characterization of surface complexes in enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Roy, D.; Furtak, T. E.

1984-11-01

An indicator molecule, para-nitrosodimethylanaline (p-NDMA), has been used to study the chemical nature of surface complexes involving the active site for SERS in the electrochemical environment. We present evidence for positively charged Ag atoms stabilized by coadsorbed Cl- ions as the primary sites which are produced during the oxidation reduction cycle treatment of an Ag electrode. Depending on the relative number of Cl- ions which influence the Ag site the active site demonstrates a greater or lesser electron accepting character toward p-NDMA. This character is influenced by the applied voltage and by the presence of Tl+ ions in the bulk of the solution near the surface. As in previously studied systems p-NDMA/Cl-/Ag complexes demonstrate charge transfer excitation which in this case is from the p-NDMA to the Ag site. These results further solidify the importance of complex formation in electrochemical SERS and suggest that caution should be applied when using SERS as a quantitative measure of surface coverage.

Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2, the first step in reduction of CO 2

DOE PAGES

Favaro, Marco; Xiao, Hai; Cheng, Tao; ...

2017-06-12

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

Improving the corrosion resistance of proton exchange membrane fuel cell carbon supports by pentafluorophenyl surface functionalization

NASA Astrophysics Data System (ADS)

Forouzandeh, Farisa; Li, Xiaoan; Banham, Dustin W.; Feng, Fangxia; Joseph Kakanat, Abraham; Ye, Siyu; Birss, Viola

2018-02-01

In this study, the effect of surface functionalization on the electrochemical corrosion resistance of a high surface area, mesoporous colloid imprinted carbon powder (CIC), as well as microporous Vulcan carbon (VC, serving as the benchmark), was demonstrated, primarily for PEM fuel cell applications. CIC-22, which is highly hydrophilic and was synthesized with 22 nm silica colloid templates, and as-received, mildly hydrophobic, VC powders, were functionalized with 2,3,4,5,6-pentafluorophenyl (-PhF5) surface groups using a straightforward diazonium reduction reaction. These carbons were then subjected to corrosion testing, involving a potential cycling-step sequence in room temperature 0.5 M H2SO4. Using cyclic voltammetry and charge/time analysis, the double layer and pseudo-capacitive gravimetric charges of the carbons, prior to and after the application of these potential steps, were tracked in order to obtain information about surface area changes and the extent of carbon oxidation, respectively. It is shown that the corrosion resistance was improved by ca. 50-80% by surface functionalization, likely due to a combination of surface passivation (loss of carbon active sites) and increased surface hydrophobicity.

Exact analysis of surface field reduction due to field-emitted vacuum space charge, in parallel-plane geometry, using simple dimensionless equations

NASA Astrophysics Data System (ADS)

Forbes, Richard G.

2008-10-01

This paper reports (a) a simple dimensionless equation relating to field-emitted vacuum space charge (FEVSC) in parallel-plane geometry, namely 9ζ2θ2-3θ-4ζ+3=0, where ζ is the FEVSC "strength" and θ is the reduction in emitter surface field (θ =field-with/field-without FEVSC), and (b) the formula j =9θ2ζ/4, where j is the ratio of emitted current density JP to that predicted by Child's law. These equations apply to any charged particle, positive or negative, emitted with near-zero kinetic energy. They yield existing and additional basic formulas in planar FEVSC theory. The first equation also yields the well-known cubic equation describing the relationship between JP and applied voltage; a method of analytical solution is described. Illustrative FEVSC effects in a liquid metal ion source and in field electron emission are discussed. For Fowler-Nordheim plots, a "turn-over" effect is predicted in the high FEVSC limit. The higher the voltage-to-local-field conversion factor for the emitter concerned, then the higher is the field at which turn over occurs. Past experiments have not found complete turn over; possible reasons are noted. For real field emitters, planar theory is a worst-case limit; however, adjusting ζ on the basis of Monte Carlo calculations might yield formulae adequate for real situations.

Integrating high electrical conductivity and photocatalytic activity in cotton fabric by cationizing for enriched coating of negatively charged graphene oxide.

PubMed

Sahito, Iftikhar Ali; Sun, Kyung Chul; Arbab, Alvira Ayoub; Qadir, Muhammad Bilal; Jeong, Sung Hoon

2015-10-05

Electroconductive textiles have attended tremendous focus recently and researchers are making efforts to increase conductivity of e-textiles, in order to increase the use of such flexible and low cost textile materials. In this study, surface conductivity and photo catalytic activity of standard cotton fabric (SCF) was enhanced by modifying its surface charge, from negative to positive, using Bovine Serum Albumin (BSA) as a cationic agent, to convert it into cationised cotton fabric (CCF). Then, both types of fabrics were dip coated with a simple dip and dry technique for the adsorption of negatively charged graphene oxide (GO) sheets onto its surface. This resulted in 67.74% higher loading amount of GO on the CCF making self-assembly. Finally, this coating was chemically converted by vapor reduction using hydrazine hydrate to reduced graphene oxide (rGO) for restoration of a high electrical conductivity at the fabric surface. Our results revealed that with such high loading of GO, the surface resistance of CCF was only 40Ω/sq as compared to 510Ω/sq of the SCF and a 66% higher photo catalytic activity was also achieved through cationization for improved GO coating. Graphene coated SCF and CCF were characterized using FE-SEM, FTIR, Raman, UV-vis, WAXD, EDX and XPS spectroscopy to ascertain successful reduction of GO to rGO. The effect of BSA treatment on adsorption of cotton fabric was studied using drop shape analyzer to measure contact angle and for thermal and mechanical resistance, the fabric was tested for TGA and tensile strength, respectively. rGO coated fabric also showed slightly improved thermal stability yet a minor loss of strength was observed. The high flexibility, photocatalytic activity and excellent conductivity of this fabric suggests that it can be used as an electrode material for various applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

NASA Astrophysics Data System (ADS)

Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; McDougall, Dan; Tringides, Michael; Ho, Kaiming

2013-12-01

The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H2 molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H2 molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoshimoto, Shinya, E-mail: yosshi@issp.u-tokyo.ac.jp; Shiozawa, Yuichiro; Koitaya, Takanori

Electronic states and electrical conductivity of the native oxide Si(111) surface adsorbed with an electron donor tetrakis(dimethylamino)ethylene (TDAE) were investigated using ultraviolet photoelectron spectroscopy, X-ray photoelectron spectroscopy (XPS), and independently driven four-probe conductivity measurements. The formation of positively charged TDAE species is confirmed by the downward shift of the vacuum level by 1.45 eV, the absence of HOMO level in the valence band, and observation of the positively charged state in the N 1s XPS spectra. Si 2p XPS spectra and four-probe conductivity measurements revealed that TDAE adsorption induces an increase in downward band bending and a reduction in electrical resistancemore » of the surface, respectively. The sheet conductivity and the electron density of the surface are 1.1 μS/◻ and 4.6 × 10{sup 9} cm{sup −2}, respectively, after TDAE adsorption, and they are as high as 350% of the original surface. These results demonstrate that the electron density of the semiconductor surface is successfully controlled by the electron donor molecule TDAE.« less

Photosensitized electron transfer processes in SiO2 colloids and sodium lauryl sulfate micellar systems: Correlation of quantum yields with interfacial surface potentials

PubMed Central

Laane, Colja; Willner, Itamar; Otvos, John W.; Calvin, Melvin

1981-01-01

The effectiveness of negatively charged colloidal SiO2 particles in controlling photosensitized electron transfer reactions has been studied and compared with that of the negatively charged sodium lauryl sulfate (NaLauSO4) micellar system. In particular, the photosensitized reduction of the zwitterionic electron acceptor propylviologen sulfonate (PVS0) with tris(2,2′-bipyridinium)ruthenium(II) [Ru(bipy)32+] as the sensitizer and triethanolamine as the electron donor is found to have a quantum yield of 0.033 for formation of the radical anion (PVS[unk]) in the SiO2 colloid compared with 0.005 in the homogeneous system and 0.0086 in a NaLauSO4 micellar solution. The higher quantum yields obtained with the SiO2 colloidal system are attributed to substantial stabilization against back reaction of the intermediate photoproducts—i.e., Ru(bipy)33+ and PVS[unk]—by electrostatic repulsion of the reduced electron acceptor from the negatively charged particle surface. The binding properties of the SiO2 particles and NaLauSO4 micelles were investigated by flow dialysis. The results show that the sensitizer binds to both interfaces and that the SiO2 interface is characterized by a much higher surface potential than the micellar interface (≈-170 mV vs. -85 mV). The effect of ionic strength on the surface potential was estimated from the Gouy-Chapman theory, and the measured quantum yields of photosensitized electron transfer were correlated with surface potential at different ionic strengths. This correlation shows that the quantum yield is not affected by surface potentials smaller than ≈-40 mV. At larger potentials, the quantum yield increases rapidly. The quantum yield obtained in the micellar system at different strengths fits nicely on the correlation curve for the colloid SiO2 system. These results indicate that the surface potential is the dominant factor in the quantum yield improvement for PVS0 reduction. PMID:16593095

Ultrasmall iron oxide nanoparticles for biomedical applications: improving the colloidal and magnetic properties.

PubMed

Costo, Rocio; Bello, Valentina; Robic, Caroline; Port, Marc; Marco, Jose F; Puerto Morales, M; Veintemillas-Verdaguer, Sabino

2012-01-10

A considerable increase in the saturation magnetization, M(s) (40%), and initial susceptibility of ultrasmall (<5 nm) iron oxide nanoparticles prepared by laser pyrolysis was obtained through an optimized acid treatment. Moreover, a significant enhancement in the colloidal properties, such as smaller aggregate sizes in aqueous media and increased surface charge densities, was found after this chemical protocol. The results are consistent with a reduction in nanoparticle surface disorder induced by a dissolution-recrystallization mechanism.

Surface Chemistry and Precursor Material Effects on the Performance of Pyrolyzed Nanofibers as Anodes for Lithium-ion Batteries

NASA Astrophysics Data System (ADS)

Loebl, Andrew James

Next-generation lithium-ion batteries to meet consumer demands and new applications require the development of new electrode materials. Electrospinning of polymers is a simple and effective method to create one-dimensional, self-supporting materials, with no inactive components after pyrolysis. Composites of these nanofibers and high-capacity lithium materials have been demonstrated to possess superior reversible capacity than state-of-the-art commercial anodes. Despite impressive reversible discharge capacities polyacrylonitrile-based composites are not ready for adoption in commercial applications. These materials suffer from irreversible losses of Li to formation on the electrode of the solid electrolyte interphase during the first charge of the cell. This thesis work has taken two approaches to engineer high-performing nanofiber-based electrodes. First, the chemistry at the interface of the electrode and the electrolyte has been changed by depositing new surfaces. Attempts to create a graphitic fiber surface via plasma enhanced chemical vapor deposition did not result in an improvement of the irreversible losses. However, the experiments did demonstrate the growth of large surface area carbon nanowalls on the pyrolyzed electrospun fibers, creating a material which could serve as a substrate in catalysis or as an electrode for composite ultra-capacitors. Additionally, passivation surfaces were deposited by atomic layer deposition and molecular layer deposition. These new surfaces were employed to reduce the irreversible consumption of lithium by moving the charge transfer reaction to the interface of the carbon and the new material. The removal the lithium from the solvent prior to charge transfer limits the irreversible reduction of solvent by metallic lithium. Alumina films grown by atomic layer deposition reduced lithium losses to the solid electrolyte interphase by up to 42% for twenty deposition cycles. This large improvement in irreversible capacity resulted in a nearly 50% reduction in reversible lithium storage. Thinner coatings of alumina had a less dramatic effect on both the irreversible capacity losses and the reversible discharge capacity. A coating of ten cycles of alumina at a temperature of 150 °C resulted in a 17% reduction in irreversible capacity with negligible impact on the reversible capacity. Hybrid aluminum-organic films grown by molecular layer deposition also reduced irreversible lithium losses. The largest reduction was 23% for electrodes coated with 40 cycles of the alucone material. For all thicknesses studied these hybrid films delivered less improvement than the alumina grown by atomic layer deposition, with poor reversible lithium storage capacity available at high charging and discharging currents. Second, polyacrylonitrile has served as the precursor for electrospun composite electrodes because of its ease of processing and well-known carbonization process. Polyimides represent a family of polymers for which the material properties can be tailored by careful monomer selection. These polymers were used as the non-woven matrix to create materials capable of delivering a larger percentage of their maximum reversible capacities at high currents when compared to polyacrylonitrile-based electrodes. These materials had a more graphitic structure based on Raman spectroscopy, and resulted in lower irreversible capacity losses than polyacrylonitrile-based fibers for fibers based on pyromellitic dianhydride and p-phenylene diamine.

High reduction of interfacial charge recombination in colloidal quantum dot solar cells by metal oxide surface passivation.

PubMed

Chang, Jin; Kuga, Yuki; Mora-Seró, Iván; Toyoda, Taro; Ogomi, Yuhei; Hayase, Shuzi; Bisquert, Juan; Shen, Qing

2015-03-12

Bulk heterojunction (BHJ) solar cells based on colloidal QDs and metal oxide nanowires (NWs) possess unique and outstanding advantages in enhancing light harvesting and charge collection in comparison to planar architectures. However, the high surface area of the NW structure often brings about a large amount of recombination (especially interfacial recombination) and limits the open-circuit voltage in BHJ solar cells. This problem is solved here by passivating the surface of the metal oxide component in PbS colloidal quantum dot solar cells (CQDSCs). By coating thin TiO2 layers onto ZnO-NW surfaces, the open-circuit voltage and power conversion efficiency have been improved by over 40% in PbS CQDSCs. Characterization by transient photovoltage decay and impedance spectroscopy indicated that the interfacial recombination was significantly reduced by the surface passivation strategy. An efficiency as high as 6.13% was achieved through the passivation approach and optimization for the length of the ZnO-NW arrays (device active area: 16 mm2). All solar cells were tested in air, and exhibited excellent air storage stability (without any performance decline over more than 130 days). This work highlights the significance of metal oxide passivation in achieving high performance BHJ solar cells. The charge recombination mechanism uncovered in this work could shed light on the further improvement of PbS CQDSCs and/or other types of solar cells.

Electrophoresis of a polarizable charged colloid with hydrophobic surface: A numerical study

NASA Astrophysics Data System (ADS)

Bhattacharyya, Somnath; Majee, Partha Sarathi

2017-04-01

We consider the electrophoresis of a charged colloid for a generalized situation in which the particle is considered to be polarizable and the surface exhibits hydrophobicity. The dielectric polarization of the particle creates a nonlinear dependence of the electrophoretic velocity on the applied electric field, and the core hydrophobicity amplifies the fluid convection in the Debye layer. Thus, a linear analysis is no longer applicable for this situation. The present analysis is based on the numerical solution of the nonlinear electrokinetic equations based on the Navier-Stokes-Nernst-Planck-Poisson equations coupled with the Laplace equation for the electric field within the dielectric particle. The hydrophobicity of the particle may influence its electric polarization by enhancing the convective transport of ions. The nonlinear effects, such as double-layer polarization and relaxation, are also influenced by the hydrophobicity of the particle surface. The present results compare well for a lower range of the applied electric field and surface charge density with the existing results for a perfectly dielectric particle with a hydrophobic surface based on the first-order perturbation analysis due to Khair and Squires [Phys. Fluids 21, 042001 (2009), 10.1063/1.3116664]. Dielectric polarization creates a reduction in particle electrophoretic velocity, and its impact is strong for a moderate range of Debye length. A quantitative measure of the nonlinear effects is demonstrated by comparing the electrophoretic velocity with an existing linear model.

Fast ion transport at a gas-metal interface

DOE PAGES

McDevitt, Christopher J.; Tang, Xian-Zhu; Guo, Zehua

2017-11-06

Fast ion transport and the resulting fusion yield reduction are computed at a gas-metal interface. The extent of fusion yield reduction is observed to depend sensitively on the charge state of the surrounding pusher material and the width of the atomically mixed region. These sensitivities suggest that idealized boundary conditions often implemented at the gas-pusher interface for the purpose of estimating fast ion loss will likely overestimate fusion reactivity reduction in several important limits. Additionally, the impact of a spatially complex material interface is investigated by considering a collection of droplets of the pusher material immersed in a DT plasma.more » It is found that for small Knudsen numbers, the extent of fusion yield reduction scales with the surface area of the material interface. As the Knudsen number is increased, but, the simple surface area scaling is broken, suggesting that hydrodynamic mix has a nontrivial impact on the extent of fast ion losses.« less

Adsorption of benzene, toluene, and xylene by two tetramethylammonium-smectites having different charge densities

USGS Publications Warehouse

Lee, Jiunn-Fwu; Mortland, Max M.; Chiou, Cary T.; Kite, Daniel E.; Boyd, Stephen A.

1990-01-01

A high-charge smectite from Arizona [cation-exchange capacity (CEC) = 120 meq/100 g] and a low-charge smectite from Wyoming (CEC = 90 meq/100 g) were used to prepare homoionic tetramethylammonium (TMA)-clay complexes. The adsorption of benzene, toluene, and o-xylene as vapors by the dry TMA-clays and as solutes from water by the wet TMA-clays was studied. The adsorption of the organic vapors by the dry TMA-smectite samples was strong and apparently consisted of interactions with both the aluminosilicate mineral surfaces and the TMA exchange ions in the interlayers. In the adsorption of organic vapors, the closer packing of TMA ions in the dry high-charge TMA-smectite, compared with the dry low-charge TMA-smectite, resulted in a somewhat higher degree of shape-selective adsorption of benzene, toluene, and xylene. In the presence of water, the adsorption capacities of both samples for the aromatic compounds were significantly reduced, although the uptake of benzene from water by the low-charge TMA-smectite was still substantial. This lower sorption capacity was accompanied by increased shape-selectivity for the aromatic compounds. The reduction in uptake and increased selectivity was much more pronounced for the water-saturated, high-charge TMA-smectite than for the low-charge TMA-smectite. Hydration of the TMA exchange ions and/or the mineral surfaces apparently reduced the accessibility of the aromatic molecules to interlamellar regions. The resulting water-induced sieving effect was greater for the high-charge TMA-smectite due to the higher density of exchanged TMA-ions. The low-charge Wyoming TMA-smectite was a highly effective adsorbent for removing benzene from water and may be useful for purifying benzene-contaminated water.

First-principles study of structure, electronic properties and stability of tungsten adsorption on TiC(111) surface with disordered vacancies

NASA Astrophysics Data System (ADS)

Ilyasov, Victor V.; Pham, Khang D.; Zhdanova, Tatiana P.; Phuc, Huynh V.; Hieu, Nguyen N.; Nguyen, Chuong V.

2017-12-01

In this paper, we systematically investigate the atomic structure, electronic and thermodynamic properties of adsorbed W atoms on the polar Ti-terminated TixCy (111) surface with different configurations of adsorptions using first principle calculations. The bond length, adsorption energy, and formation energy for different reconstructions of the atomic structure of the W/TixCy (111) systems were established. The effect of the tungsten coverage on the electronic structure and the adsorption mechanism of tungsten atom on the TixCy (111) are also investigated. We also suggest the possible mechanisms of W nucleation on the TixCy (111) surface. The effective charges on W atoms and nearest-neighbor atoms in the examined reconstructions were identified. Additionally, we have established the charge transfer from titanium atom to tungsten and carbon atoms which determine by the reconstruction of the local atomic and electronic structures. Our calculations showed that the charge transfer correlates with the electronegativity of tungsten and nearest-neighbor atoms. We also determined the effective charge per atom of titanium, carbon atoms, and neighboring adsorbed tungsten atom in different binding configurations. We found that, with reduction of the lattice symmetry associated with titanium and carbon vacancies, the adsorption energy increases by 1.2 times in the binding site A of W/TixCy systems.

High-performance serial block-face SEM of nonconductive biological samples enabled by focal gas injection-based charge compensation.

PubMed

Deerinck, T J; Shone, T M; Bushong, E A; Ramachandra, R; Peltier, S T; Ellisman, M H

2018-05-01

A longstanding limitation of imaging with serial block-face scanning electron microscopy is specimen surface charging. This charging is largely due to the difficulties in making biological specimens and the resins in which they are embedded sufficiently conductive. Local accumulation of charge on the specimen surface can result in poor image quality and distortions. Even minor charging can lead to misalignments between sequential images of the block-face due to image jitter. Typically, variable-pressure SEM is used to reduce specimen charging, but this results in a significant reduction to spatial resolution, signal-to-noise ratio and overall image quality. Here we show the development and application of a simple system that effectively mitigates specimen charging by using focal gas injection of nitrogen over the sample block-face during imaging. A standard gas injection valve is paired with a precisely positioned but retractable application nozzle, which is mechanically coupled to the reciprocating action of the serial block-face ultramicrotome. This system enables the application of nitrogen gas precisely over the block-face during imaging while allowing the specimen chamber to be maintained under high vacuum to maximise achievable SEM image resolution. The action of the ultramicrotome drives the nozzle retraction, automatically moving it away from the specimen area during the cutting cycle of the knife. The device described was added to a Gatan 3View system with minimal modifications, allowing high-resolution block-face imaging of even the most charge prone of epoxy-embedded biological samples. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.

DNA Electrochemistry with Tethered Methylene Blue

PubMed Central

Pheeney, Catrina G.

2012-01-01

Methylene blue (MB′), covalently attached to DNA through a flexible C12 alkyl linker, provides a sensitive redox reporter in DNA electrochemistry measurements. Tethered, intercalated MB′ is reduced through DNA-mediated charge transport; the incorporation of a single base mismatch at position 3, 10, or 14 of a 17-mer causes an attenuation of the signal to 62 ± 3% of the well-matched DNA, irrespective of position in the duplex. The redox signal intensity for MB′–DNA is found to be least 3-fold larger than that of Nile blue (NB)–DNA, indicating that MB′ is even more strongly coupled to the π-stack. The signal attenuation due to an intervening mismatch does, however, depend on DNA film density and the backfilling agent used to passivate the surface. These results highlight two mechanisms for reduction of MB′ on the DNA-modified electrode: reduction mediated by the DNA base pair stack and direct surface reduction of MB′ at the electrode. These two mechanisms are distinguished by their rates of electron transfer that differ by 20-fold. The extent of direct reduction at the surface can be controlled by assembly and buffer conditions. PMID:22512327

Possible method for diagnosing waves in dusty plasmas with magnetized charged dust particulates

NASA Astrophysics Data System (ADS)

Rosenberg, M.; Shukla, P. K.

2005-05-01

We discuss theoretically a possible method for diagnosing some features of dust wave behavior in a magnetized plasma containing small (tens of nm) charged dust grains whose motion is magnetized. It is easier to magnetize a small dust particle because its charge-to-mass ratio increases as its size decreases. However, it is more difficult to use the backscattering of light from the dust as a diagnostic as the dust size decreases below the diffraction limit. The idea proposed here is to measure the reduction in transmitted UV or optical light intensity due to enhanced extinction by small metal dust particles that have surface plasmon resonances at those wavelengths. Such measurements could indicate the spatial location of the dust density compressions or rarefactions, which may yield information on the dust wave behavior, or perhaps even charged dust transport. Parameters that may be relevant to possible laboratory dusty plasma experiments are discussed.

Salt induced reduction of lysozyme adsorption at charged interfaces

NASA Astrophysics Data System (ADS)

Göhring, Holger; Paulus, Michael; Salmen, Paul; Wirkert, Florian; Kruse, Theresa; Degen, Patrick; Stuhr, Susan; Rehage, Heinz; Tolan, Metin

2015-06-01

A study of lysozyme adsorption below a behenic acid membrane and at the solid-liquid interface between aqueous lysozyme solution and a silicon wafer in the presence of sodium chloride is presented. The salt concentration was varied between 1 mmol L-1 and 1000 mmol L-1. X-ray reflectivity data show a clear dependence of the protein adsorption on the salt concentration. Increasing salt concentrations result in a decreased protein adsorption at the interface until a complete suppression at high concentrations is reached. This effect can be attributed to a reduced attractive electrostatic interaction between the positively charged proteins and negatively charged surfaces by charge screening. The measurements at the solid-liquid interfaces show a transition from unoriented order of lysozyme in the adsorbed film to an oriented order with the short protein axis perpendicular to the solid-liquid interface with rising salt concentration.

Alteration by prolactin of surface charge and membrane fluidity of rat 13762 mammary ascites tumor cells.

PubMed

Zarkower, D A; Plank, L D; Kunze, E; Keith, A; Todd, P; Hymer, W C

1984-03-01

Intraperitoneal injection of ovine prolactin (100 micrograms/d) in Fischer 344 rats bearing transplantable 13762 mammary ascites tumor (MAT) cells modifies the surface charge density and membrane fluidity of the tumor cells. In each of five experiments the mean electrophoretic mobility (epm) of MAT cells taken from prolactin-treated rats was significantly lower than that of cells from nonhormone-treated controls. Prolactin concentrations were increased in vivo by (a) direct intraperitoneal injection of ovine prolactin; (b) subcutaneous implantation of diethylstilbestrol-containing silastic capsules to produce pituitary prolactin secreting tumors; or (c) a single subcutaneous injection of polyestradiol phosphate, a long-acting estrogen. In an effort to establish that the prolactin effect was a direct one, two in vivo protocols were used: (a) MAT cells were coincubated with anterior pituitary halves obtained from nontumor-bearing littermates; or (b) rat or ovine prolactin was added to serum-free culture media containing MAT cells. In both protocols, the epm of the prolactin-treated cells was significantly lower. The isoelectric focusing pH of whole cells was increased by prolactin treatment from 4.93 to 5.12, consistent with a reduction in the number of surface carboxyl groups. The fluidity of membranes of treated cells was drastically increased, as measured by spin-label probe rotation rates. These combined results imply that the hormone exerts its effect by stimulating events in the cell that lead to a reduction of the average density of carboxylic acid residues on the tumor cell surface.

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis.

PubMed

Dinda, Enakshi; Rashid, Md Harunar; Biswas, Mrinmoy; Mandal, Tarun K

2010-11-16

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.

Heat Treatment of Tantalum and Niobium Powders Prepared by Magnesium-Thermic Reduction

NASA Astrophysics Data System (ADS)

Orlov, V. M.; Prokhorova, T. Yu.

2017-11-01

Changes in the specific surface area and porous structure of tantalum and niobium powders, which were prepared by magnesium-thermic reduction of Ta2O5, Mg4Ta2O9, and Mg4Nb2O9 oxide compounds and subjected to heat treatments at temperatures of 600-1500°C, have been studied. It is noted that, owing to the mesoporous structure of the magnesium-thermic powders, the decrease in the surface area during heat treatment, first of all, is related to a decrease in the amount of pores less than 10 nm in size. The heat treatment of a reacting mass is shown to allow us to correct the specific surface area of the powder without any increase in the oxygen content in it. Data on the effect of heat treatment conditions on the specific charge of capacitor anodes are reported.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Favaro, Marco; Xiao, Hai; Cheng, Tao

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

In vitro imaging of cells using peptide-conjugated quantum dots

NASA Astrophysics Data System (ADS)

Ishikawa, Mitsuru; Biju, Vasudevan

2010-02-01

Efficient intracellular delivery of quantum dots (QDs) in living cells and elucidating the mechanism of the delivery are essential for advancing the applications of QDs to in vivo imaging and in vivo photodynamic therapy. Here, we demonstrate that clathrin-mediated endocytosis is the most dominant pathway for the delivery of peptide-conjugated QDs. We selected an insect neuropeptide, allatostatin (AST1), conjugated with CdSe-ZnS QDs, and investigated the delivery of the conjugate in living cells. We evaluated the contributions of clathrin-mediated endocytosis, receptormediated endocytosis, and charge-based cell penetration to the delivery of QD605-AST1 conjugates by flow cytometry and fluorescence video microscopy. The delivery was suppressed by ~57% in inhibiting phosphoinositide 3-kinase with wortmannin, which blocks the formation of clathrin-coated vesicles, and by ~45% in incubating the cells at 4°C. Also, we identified clathrin-mediated endocytosis by two-color experiment to find colocalization of QD560-labeled clathrin heavy-chain antibody and QD605-AST1. We further observed reduction of the galanin receptor-mediated delivery of QD605-AST1 by ~8% in blocking the cells with a galanin antagonist, and reduction of charge-based cell penetration delivery by ~30% in removing the positive charge in the peptide from arginine and suppressing the cell-surface negative charge from glycosaminoglycan.

Aflatoxin Toxicity Reduction in Feed by Enhanced Binding to Surface-Modified Clay Additives

PubMed Central

Jaynes, William F.; Zartman, Richard E.

2011-01-01

Animal feeding studies have demonstrated that clay additives, such as bentonites, can bind aflatoxins in ingested feed and reduce or eliminate the toxicity. Bentonite deposits are found throughout the world and mostly consist of expandable smectite minerals, such as montmorillonite. The surfaces of smectite minerals can be treated with organic compounds to create surface-modified clays that more readily bind some contaminants than the untreated clay. Montmorillonites treated with organic cations, such as hexadecyltrimethylammonium (HDTMA) and phenyltrimethylammonium (PTMA), more effectively remove organic contaminants, such as benzene and toluene, from water than untreated clay. Similarly, montmorillonite treated with PTMA (Kd = 24,100) retained more aflatoxin B1 (AfB1) from aqueous corn flour than untreated montmorillonite (Kd = 944). Feed additives that reduced aflatoxin toxicity in animal feeding studies adsorbed more AfB1 from aqueous corn flour than feed additives that were less effective. The organic cations HDTMA and PTMA are considered toxic and would not be suitable for clay additives used in feed or food, but other non-toxic or nutrient compounds can be used to prepare surface-modified clays. Montmorillonite (SWy) treated with choline (Kd = 13,800) and carnitine (Kd = 3960) adsorbed much more AfB1 from aqueous corn flour than the untreated clay (Kd = 944). A choline-treated clay prepared from a reduced-charge, high-charge montmorillonite (Kd = 20,100) adsorbed more AfB1 than the choline-treated high-charge montmorillonite (Kd = 1340) or the untreated montmorillonite (Kd = 293). Surface-modified clay additives prepared using low-charge smectites and nutrient or non-toxic organic compounds might be used to more effectively bind aflatoxins in contaminated feed or food and prevent toxicity. PMID:22069725

Aflatoxin toxicity reduction in feed by enhanced binding to surface-modified clay additives.

PubMed

Jaynes, William F; Zartman, Richard E

2011-06-01

Animal feeding studies have demonstrated that clay additives, such as bentonites, can bind aflatoxins in ingested feed and reduce or eliminate the toxicity. Bentonite deposits are found throughout the world and mostly consist of expandable smectite minerals, such as montmorillonite. The surfaces of smectite minerals can be treated with organic compounds to create surface-modified clays that more readily bind some contaminants than the untreated clay. Montmorillonites treated with organic cations, such as hexadecyltrimethylammonium (HDTMA) and phenyltrimethylammonium (PTMA), more effectively remove organic contaminants, such as benzene and toluene, from water than untreated clay. Similarly, montmorillonite treated with PTMA (K(d) = 24,100) retained more aflatoxin B1 (AfB1) from aqueous corn flour than untreated montmorillonite (K(d) = 944). Feed additives that reduced aflatoxin toxicity in animal feeding studies adsorbed more AfB1 from aqueous corn flour than feed additives that were less effective. The organic cations HDTMA and PTMA are considered toxic and would not be suitable for clay additives used in feed or food, but other non-toxic or nutrient compounds can be used to prepare surface-modified clays. Montmorillonite (SWy) treated with choline (K(d) = 13,800) and carnitine (K(d) = 3960) adsorbed much more AfB1 from aqueous corn flour than the untreated clay (K(d) = 944). A choline-treated clay prepared from a reduced-charge, high-charge montmorillonite (K(d) = 20,100) adsorbed more AfB1 than the choline-treated high-charge montmorillonite (K(d) = 1340) or the untreated montmorillonite (K(d) = 293). Surface-modified clay additives prepared using low-charge smectites and nutrient or non-toxic organic compounds might be used to more effectively bind aflatoxins in contaminated feed or food and prevent toxicity.

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

PubMed

Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

2016-10-26

Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNi x Mn y Co 1-x-y O 2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni 2+ (active) and Co 3+ (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive 7 Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to the electrochemical cycling effect, electrolyte exposure also shows non-negligible influence on cathode surface degradation. These chemical and structural changes of the NMC cathode could contribute to the first-cycle coulombic inefficiency, restrict the charge transfer characteristics and ultimately impact the cell capacity.

Role of LiCoO 2 Surface Terminations in Oxygen Reduction and Evolution Kinetics

DOE PAGES

Han, Binghong; Qian, Danna; Risch, Marcel; ...

2015-03-22

Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of LiCoO 2 nanorods with sizes in the range from 9 to 40 nm were studied in alkaline solution. The sides of these nanorods were terminated with low-index surfaces such as (003) while the tips were terminated largely with high-index surfaces such as (104) as revealed by high-resolution transmission electron microscopy. Electron energy loss spectroscopy demonstrated that low-spin Co 3+ prevailed on the sides, while the tips exhibited predominantly high- or intermediate-spin Co 3+. We correlated the electronic and atomic structure to higher specific ORR and OER activities at themore » tips as compared to the sides, which was accompanied by more facile redox of Co 2+/3+ and higher charge transferred per unit area. These findings highlight the critical role of surface terminations and electronic structures of transition metal oxides on the ORR and OER activity.« less

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Ambipolar surface state thermoelectric power of topological insulator Bi2Se3.

PubMed

Kim, Dohun; Syers, Paul; Butch, Nicholas P; Paglione, Johnpierre; Fuhrer, Michael S

2014-01-01

We measure gate-tuned thermoelectric power of mechanically exfoliated Bi2Se3 thin films in the topological insulator regime. The sign of the thermoelectric power changes across the charge neutrality point as the majority carrier type switches from electron to hole, consistent with the ambipolar electric field effect observed in conductivity and Hall effect measurements. Near the charge neutrality point and at low temperatures, the gate-dependent thermoelectric power follows the semiclassical Mott relation using the expected surface state density of states but is larger than expected at high electron doping, possibly reflecting a large density of states in the bulk gap. The thermoelectric power factor shows significant enhancement near the electron-hole puddle carrier density ∼0.5 × 10(12) cm(-2) per surface at all temperatures. Together with the expected reduction of lattice thermal conductivity in low-dimensional structures, the results demonstrate that nanostructuring and Fermi level tuning of three-dimensional topological insulators can be promising routes to realize efficient thermoelectric devices.

Vapor-phase-processed fluorinated self-assembled monolayer for organic thin-film transistors

NASA Astrophysics Data System (ADS)

Roh, Jeongkyun; Lee, Changhee; Kwak, Jeonghun; Jung, Byung Jun; Kim, Hyeok

2015-09-01

A vapor-phase-processed fluorinated silazane self-assembled monolayer (SAM), 1,3-bis(trifluoropropyl)-1,1,3,3-tetramethyldisilazane (FPDS), was introduced as a surface modifier for pentacene-based organic thin-film transistors (OTFTs). A remarkable improvement in the field effect mobility from 0.25 cm2/Vs (without SAM-treatment) to 0.42 cm2/Vs (with FPDS-treatment) was observed, which was attributed to the better pentacene growth on a hydrophobic surface. A significant reduction in the contact resistance was also observed by FPDS treatment due to the improved bulk conductivity and diminished charge trapping at the gate dielectric surface by the SAM treatment. In addition, FPDS treatment efficiently improved the bias stability of the OTFTs; the drain-to-source current degradation by the bias stress was greatly reduced from 80% to 50% by FPDS treatment, and the characteristic time for charge trapping of the FPDS treated OTFTs was approximately one order of magnitude larger than that of the OTFTs without SAM treatment.

Balancing charge in the complementarity-determining regions of humanized mAbs without affecting pI reduces non-specific binding and improves the pharmacokinetics.

PubMed

Datta-Mannan, Amita; Thangaraju, Arunkumar; Leung, Donmienne; Tang, Ying; Witcher, Derrick R; Lu, Jirong; Wroblewski, Victor J

2015-01-01

Lowering the isoelectric point (pI) through engineering the variable region or framework of an IgG can improve its exposure and half-life via a reduction in clearance mediated through non-specific interactions. As such, net charge is a potentially important property to consider in developing therapeutic IgG molecules having favorable pharmaceutical characteristics. Frequently, it may not be possible to shift the pI of monoclonal antibodies (mAbs) dramatically without the introduction of other liabilities such as increased off-target interactions or reduced on-target binding properties. In this report, we explored the influence of more subtle modifications of molecular charge on the in vivo properties of an IgG1 and IgG4 monoclonal antibody. Molecular surface modeling was used to direct residue substitutions in the complementarity-determining regions (CDRs) to disrupt positive charge patch regions, resulting in a reduction in net positive charge without affecting the overall pI of the mAbs. The effect of balancing the net positive charge on non-specific binding was more significant for the IgG4 versus the IgG1 molecule that we examined. This differential effect was connected to the degree of influence on cellular degradation in vitro and in vivo clearance, distribution and metabolism in mice. In the more extreme case of the IgG4, balancing the charge yielded an ∼7-fold improvement in peripheral exposure, as well as significantly reduced tissue catabolism and subsequent excretion of proteolyzed products in urine. Balancing charge on the IgG1 molecule had a more subtle influence on non-specific binding and yielded only a modest alteration in clearance, distribution and elimination. These results suggest that balancing CDR charge without affecting the pI can lead to improved mAb pharmacokinetics, the magnitude of which is likely dependent on the relative influence of charge imbalance and other factors affecting the molecule's disposition.

Balancing charge in the complementarity-determining regions of humanized mAbs without affecting pI reduces non-specific binding and improves the pharmacokinetics

PubMed Central

Datta-Mannan, Amita; Thangaraju, Arunkumar; Leung, Donmienne; Tang, Ying; Witcher, Derrick R; Lu, Jirong; Wroblewski, Victor J

2015-01-01

Lowering the isoelectric point (pI) through engineering the variable region or framework of an IgG can improve its exposure and half-life via a reduction in clearance mediated through non-specific interactions. As such, net charge is a potentially important property to consider in developing therapeutic IgG molecules having favorable pharmaceutical characteristics. Frequently, it may not be possible to shift the pI of monoclonal antibodies (mAbs) dramatically without the introduction of other liabilities such as increased off-target interactions or reduced on-target binding properties. In this report, we explored the influence of more subtle modifications of molecular charge on the in vivo properties of an IgG1 and IgG4 monoclonal antibody. Molecular surface modeling was used to direct residue substitutions in the complementarity-determining regions (CDRs) to disrupt positive charge patch regions, resulting in a reduction in net positive charge without affecting the overall pI of the mAbs. The effect of balancing the net positive charge on non-specific binding was more significant for the IgG4 versus the IgG1 molecule that we examined. This differential effect was connected to the degree of influence on cellular degradation in vitro and in vivo clearance, distribution and metabolism in mice. In the more extreme case of the IgG4, balancing the charge yielded an ∼7-fold improvement in peripheral exposure, as well as significantly reduced tissue catabolism and subsequent excretion of proteolyzed products in urine. Balancing charge on the IgG1 molecule had a more subtle influence on non-specific binding and yielded only a modest alteration in clearance, distribution and elimination. These results suggest that balancing CDR charge without affecting the pI can lead to improved mAb pharmacokinetics, the magnitude of which is likely dependent on the relative influence of charge imbalance and other factors affecting the molecule's disposition. PMID:25695748

Photoactivity of N-doped ZnO nanoparticles in oxidative and reductive reactions

NASA Astrophysics Data System (ADS)

Oliveira, Jéssica A.; Nogueira, André E.; Gonçalves, Maria C. P.; Paris, Elaine C.; Ribeiro, Caue; Poirier, Gael Y.; Giraldi, Tania R.

2018-03-01

N-doped ZnO is a prospective material for photocatalytic reactions. However, only oxidative paths are well investigated in the literature. This paper describes a comparative study about ZnO and ZnO:N potential for oxidative and reductive reactions, probed by rhodamine B dye photodegradation and CO2 photoreduction. The materials were prepared by the polymeric precursor method, using urea as a nitrogen source, and different heat treatments were used to observe their effects on surface decontamination, crystallinity, particle sizes and shapes, and photocatalytic performance. ZnO and ZnO:N presented a wurtzite crystalline structure and nanometric-scale particles. Samples submitted to higher temperatures showed lower specific surface areas, but higher crystallinity and lower contents of species adsorbed on their surfaces. On the other hand, the photocatalysts annealed in shorter times presented smaller crystallite sizes and lower crystallinity. These factors influenced the photoactivity in both conditions, i.e., oxidation and reduction reactions, under the ultraviolet and visible light, indicating that structural factors influenced the adequate charge separation and consequent photocatalytic activity since the as-synthesized samples were versatile photocatalysts in both redox reactions.

Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces.

PubMed

Wen, Bao-Ying; Jin, Xi; Li, Yue; Wang, Ya-Hao; Li, Chao-Yu; Liang, Miao-Miao; Panneerselvam, Rajapandiyan; Xu, Qing-Chi; Wu, De-Yin; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2016-06-21

For the first time, we used the electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) technique to in situ characterize the adsorption behaviour of four DNA bases (adenine, guanine, thymine, and cytosine) on atomically flat Au(111) electrode surfaces. The spectroscopic results of the various molecules reveal similar features, such as the adsorption-induced reconstruction of the Au(111) surface and the drastic Raman intensity reduction of the ring breathing modes after the lifting reconstruction. As a preliminary study of the photo-induced charge transfer (PICT) mechanism, the in situ spectroscopic results obtained on single crystal surfaces are excellently illustrated with electrochemical data.

A universal steady state I-V relationship for membrane current

NASA Technical Reports Server (NTRS)

Chernyak, Y. B.; Cohen, R. J. (Principal Investigator)

1995-01-01

A purely electrical mechanism for the gating of membrane ionic channel gives rise to a simple I-V relationship for membrane current. Our approach is based on the known presence of gating charge, which is an established property of the membrane channel gating. The gating charge is systematically treated as a polarization of the channel protein which varies with the external electric field and modifies the effective potential through which the ions migrate in the channel. Two polarization effects have been considered: 1) the up or down shift of the whole potential function, and 2) the change in the effective electric field inside the channel which is due to familiar effect of the effective reduction of the electric field inside a dielectric body because of the presence of surface charges on its surface. Both effects are linear in the channel polarization. The ionic current is described by a steady state solution of the Nernst-Planck equation with the potential directly controlled by the gating charge system. The solution describes reasonably well the steady state and peak-current I-V relationships for different channels, and when applied adiabatically, explains the time lag between the gating charge current and the rise of the ionic current. The approach developed can be useful as an effective way to model the ionic currents in axons, cardiac cells and other excitable tissues.

Redox control of ferrocene-based complexes with systematically extended π-conjugated connectors: switchable and tailorable second order nonlinear optics.

PubMed

Wang, Wen-Yong; Ma, Na-Na; Sun, Shi-Ling; Qiu, Yong-Qing

2014-03-14

The studies of geometrical structures, thermal stabilities, redox properties, nonlinear responses and optoelectronic properties have been carried out on a series of novel ferrocenyl (Fc) chromophores with the view of assessing their switchable and tailorable second order nonlinear optics (NLO). The use of a constant Fc donor and a 4,4'-bipyridinium acceptor and varied conjugated bridges makes it possible to systematically determine the contribution of organic connectors to chromophore nonlinear optical activities. The structures reveal that both the reduction reactions and organic connectors have a significant influence on 4,4'-bipyridinium. The potential energy surface maps along with plots of reduced density gradient mirror the thermal stabilities of the Fc-based chromophores. The first and second reductions take place preferentially at the 4,4'-bipyridinium moieties. Significantly, the reduction processes result in the molecular switches with large NLO contrast varying from zero or very small to a large value. Moreover, time-dependent density functional theory results indicate that the absorption peaks are mainly attributed to Fc to 4,4'-bipyridinium charge transfer and the mixture of intramolecular charge transfer within the two respective 4,4'-bipyridinium moieties coupled with interlayer charge transfer between the two 4,4'-bipyridinium moieties. This provides us with comprehensive information on the effect of organic connectors on the NLO properties.

Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO 2 reduction

DOE PAGES

Hoch, Laura B.; Szymanski, Paul; Ghuman, Kulbir Kaur; ...

2016-11-28

In 2O 3-x(OH) y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO 2 to CO via the reverse water–gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In 2O 3-x(OH) y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play amore » significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO 2 reduction.« less

Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO 2 reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoch, Laura B.; Szymanski, Paul; Ghuman, Kulbir Kaur

In 2O 3-x(OH) y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO 2 to CO via the reverse water–gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In 2O 3-x(OH) y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play amore » significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO 2 reduction.« less

Surface charge accumulation of solid insulator under nanosecond pulse in vacuum: 3D distribution features and mechanism

NASA Astrophysics Data System (ADS)

Qi, Bo; Gao, Chunjia; Sun, Zelai; Li, Chengrong

2017-11-01

Surface charge accumulation can incur changes in electric field distribution, involved in the electron propagation process, and result in a significant decrease in the surface flashover voltage. The existing 2D surface charge measurement fails to meet the actual needs in real engineering applications that usually adopt the 45° conical frustum insulators. The present research developed a novel 3D measurement platform to capture surface charge distribution on solid insulation under nanosecond pulse in a vacuum. The results indicate that all surface charges are positive under a positive pulse and negative under a negative pulse. Surface charges tend to accumulate more near the upper electrode. Surface charge density increases significantly with the increase in pulse counts and amplitudes. Accumulation of surface charge results in a certain decrease of flashover voltage. Taking consideration of the secondary electron emission for the surface charge accumulation, four materials were obtained to demonstrate the effects on surface charge. Combining the effect incurred by secondary electron emission and the weighty action taken by surface charge accumulation on the flashover phenomena, the discharge mechanism along the insulator surface under nanosecond pulse voltage was proposed.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

NASA Astrophysics Data System (ADS)

Ryu, S.; Zhou, H.; Paudel, T. R.; Irwin, J.; Podkaminer, J. P.; Bark, C. W.; Lee, D.; Kim, T. H.; Fong, D. D.; Rzchowski, M. S.; Tsymbal, E. Y.; Eom, C. B.

2017-10-01

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internal structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.

In-situ probing of coupled atomic restructuring and metallicity of oxide heterointerfaces induced by polar adsorbates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryu, S.; Zhou, H.; Paudel, T. R.

Microscopic understanding of the surface-controlled conductivity of the two dimensional electron gas at complex oxide interfaces is crucial for developing functional interfaces. We observe conductivity and structural modification using in-situ synchrotron surface x-ray diffraction as the surface of a model LaAlO3/SrTiO3 (001) heterostructure is changed by polar adsorbates. We find that polar adsorbate-induced interfacial metallicity reduces polar distortions in the LaAlO3 layer. First-principles density functional theory calculations show that surface dipoles introduced by polar adsorbates lead to additional charge transfer and the reduction of polar displacements in the LaAlO3 layer, consistent with the experimental observations. Our study supports that internalmore » structural deformations controlling functionalities can be driven without the application of direct electrical or thermal bias and offers a route to tuning interfacial properties. These results also highlight the important role of in-situ x-ray scattering with atomic resolution in capturing and exploring structural distortions and charge density changes caused by external perturbations such as chemical adsorption, redox reaction, and generation and/or annihilation of surface defects.« less

Enhanced photoelectrochemical water splitting performance of anodic TiO(2) nanotube arrays by surface passivation.

PubMed

Gui, Qunfang; Xu, Zhen; Zhang, Haifeng; Cheng, Chuanwei; Zhu, Xufei; Yin, Min; Song, Ye; Lu, Linfeng; Chen, Xiaoyuan; Li, Dongdong

2014-10-08

One-dimensional anodic titanium oxide nanotube (TONT) arrays provide a direct pathway for charge transport, and thus hold great potential as working electrodes for electrochemical energy conversion and storage devices. However, the prominent surface recombination due to the large amount surface defects hinders the performance improvement. In this work, the surface states of TONTs were passivated by conformal coating of high-quality Al2O3 onto the tubular structures using atomic layer deposition (ALD). The modified TONT films were subsequently employed as anodes for photoelectrochemical (PEC) water splitting. The photocurrent (0.5 V vs Ag/AgCl) recorded under air mass 1.5 global illumination presented 0.8 times enhancement on the electrode with passivation coating. The reduction of surface recombination rate is responsible for the substantially improved performance, which is proposed to have originated from a decreased interface defect density in combination with a field-effect passivation induced by a negative fixed charge in the Al2O3 shells. These results not only provide a physical insight into the passivation effect, but also can be utilized as a guideline to design other energy conversion devices.

Oral insulin delivery, the challenge to increase insulin bioavailability: Influence of surface charge in nanoparticle system.

PubMed

Czuba, Elodie; Diop, Mouhamadou; Mura, Carole; Schaschkow, Anais; Langlois, Allan; Bietiger, William; Neidl, Romain; Virciglio, Aurélien; Auberval, Nathalie; Julien-David, Diane; Maillard, Elisa; Frere, Yves; Marchioni, Eric; Pinget, Michel; Sigrist, Séverine

2018-05-05

Oral administration of insulin increases patient comfort and could improve glycemic control thanks to the hepatic first passage. However, challenges remain. The current approach uses poly (d, lactic-co-glycolic) acid (PLGA) nanoparticles (NPs), an effective drug carrier system with a long acting profile. However, this system presents a bioavailability of less than 20% for insulin encapsulation. In this context, physico-chemical parameters like surface charge could play a critical role in NP uptake by the intestinal barrier. Therefore, we developed a simple method to modulate NP surface charge to test its impact on uptake in vitro and finally on NP efficiency in vivo. Various NPs were prepared in the presence (+) or absence (-) of polyvinyl alcohol (PVA), sodium dodecyl sulfate (SDS), and/or coated with chitosan chloride. In vitro internalization was tested using epithelial culture of Caco-2 or using a co-culture (Caco-2/RevHT29MTX) by flow cytometry. NPs were then administered by oral route using a pharmaceutical complex vector (100 or 250 UI/kg) in a diabetic rat model. SDS-NPs (-42 ± 2 mV) were more negatively charged than -PVA-NPs (-22 ± 1 mV) and chitosan-coated NPs were highly positively charged (56 ± 2 mV) compared to +PVA particles (-2 ± 1 mV), which were uncharged. In the Caco-2 model, NP internalization was significantly improved by using negatively charged NPs (SDS NPs) compared to using classical NPs (+PVA NPs) and chitosan-coated NPs. Finally, the efficacy of insulin SDS-NPs was demonstrated in vivo (100 or 250 UI insulin/kg) with a reduction of blood glucose levels in diabetic rats. Formulation of negatively charged NPs represents a promising approach to improve NP uptake and insulin bioavailability for oral delivery. Copyright © 2018 Elsevier B.V. All rights reserved.

Carbon nanotubes' surface chemistry determines their potency as vaccine nanocarriers in vitro and in vivo

PubMed Central

Hassan, Hatem A.F.M.; Smyth, Lesley; Rubio, Noelia; Ratnasothy, Kulachelvy; Wang, Julie T.-W.; Bansal, Sukhvinder S.; Summers, Huw D.; Diebold, Sandra S.; Lombardi, Giovanna; Al-Jamal, Khuloud T.

2016-01-01

Carbon nanotubes (CNTs) have shown marked capabilities in enhancing antigen delivery to antigen presenting cells. However, proper understanding of how altering the physical properties of CNTs may influence antigen uptake by antigen presenting cells, such as dendritic cells (DCs), has not been established yet. We hypothesized that altering the physical properties of multi-walled CNTs (MWNTs)-antigen conjugates, e.g. length and surface charge, can affect the internalization of MWNT-antigen by DCs, hence the induced immune response potency. For this purpose, pristine MWNTs (p-MWNTs) were exposed to various chemical reactions to modify their physical properties then conjugated to ovalbumin (OVA), a model antigen. The yielded MWNTs-OVA conjugates were long MWNT-OVA (~ 386 nm), bearing net positive charge (5.8 mV), or short MWNTs-OVA (~ 122 nm) of increasing negative charges (− 23.4, − 35.8 or − 39 mV). Compared to the short MWNTs-OVA bearing high negative charges, short MWNT-OVA with the lowest negative charge demonstrated better cellular uptake and OVA-specific immune response both in vitro and in vivo. However, long positively-charged MWNT-OVA showed limited cellular uptake and OVA specific immune response in contrast to short MWNT-OVA displaying the least negative charge. We suggest that reduction in charge negativity of MWNT-antigen conjugate enhances cellular uptake and thus the elicited immune response intensity. Nevertheless, length of MWNT-antigen conjugate might also affect the cellular uptake and immune response potency; highlighting the importance of physical properties as a consideration in designing a MWNT-based vaccine delivery system. PMID:26802552

Hospital charges associated with motorcycle crash factors: a quantile regression analysis.

PubMed

Olsen, Cody S; Thomas, Andrea M; Cook, Lawrence J

2014-08-01

Previous studies of motorcycle crash (MC) related hospital charges use trauma registries and hospital records, and do not adjust for the number of motorcyclists not requiring medical attention. This may lead to conservative estimates of helmet use effectiveness. MC records were probabilistically linked with emergency department and hospital records to obtain total hospital charges. Missing data were imputed. Multivariable quantile regression estimated reductions in hospital charges associated with helmet use and other crash factors. Motorcycle helmets were associated with reduced median hospital charges of $256 (42% reduction) and reduced 98th percentile of $32,390 (33% reduction). After adjusting for other factors, helmets were associated with reductions in charges in all upper percentiles studied. Quantile regression models described homogenous and heterogeneous associations between other crash factors and charges. Quantile regression comprehensively describes associations between crash factors and hospital charges. Helmet use among motorcyclists is associated with decreased hospital charges. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

PubMed

Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

2015-01-21

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Adsorption of cellular peptides of Microcystis aeruginosa and two herbicides onto activated carbon: effect of surface charge and interactions.

PubMed

Hnatukova, Petra; Kopecka, Ivana; Pivokonsky, Martin

2011-05-01

In this research, the adsorption of two herbicides, alachlor (ALA) and terbuthylazine (TBA), on granular activated carbon (GAC) in the presence of well-characterized peptide fraction of cellular organic matter (COM) produced by cyanobacterium Microcystis aeruginosa was studied. Two commercially available GACs were characterized using nitrogen gas adsorption and surface charge titrations. The COM peptides of molecular weight (MW) < 10 kDa were isolated and characterized using MW fractionation technique and high-performance size exclusion chromatography (HPSEC). The effect of surface charge on the adsorption of COM peptides was studied by means of equilibrium adsorption experiments at pH 5 and pH 8.5. Electrostatic interactions and hydrogen bonding proved to be important mechanisms of COM peptides adsorption. The adsorption of ALA and TBA on granular activated carbon preloaded with COM peptides was influenced by solution pH. The reduction in adsorption was significantly greater at pH 5 compared to pH 8.5, which corresponded to the increased adsorption of COM peptides at pH 5. The majority of the competition between COM peptides and both herbicides was attributed to low molecular weight COM peptides with MW of 700, 900, 1300 and 1700 Da. Copyright © 2011 Elsevier Ltd. All rights reserved.

An autonomous photosynthetic device in which all charge carriers derive from surface plasmons.

PubMed

Mubeen, Syed; Lee, Joun; Singh, Nirala; Krämer, Stephan; Stucky, Galen D; Moskovits, Martin

2013-04-01

Solar conversion to electricity or to fuels based on electron-hole pair production in semiconductors is a highly evolved scientific and commercial enterprise. Recently, it has been posited that charge carriers either directly transferred from the plasmonic structure to a neighbouring semiconductor (such as TiO₂) or to a photocatalyst, or induced by energy transfer in a neighbouring medium, could augment photoconversion processes, potentially leading to an entire new paradigm in harvesting photons for practical use. The strong dependence of the wavelength at which the local surface plasmon can be excited on the nanostructure makes it possible, in principle, to design plasmonic devices that can harvest photons over the entire solar spectrum and beyond. So far, however, most such systems show rather small photocatalytic activity in the visible as compared with the ultraviolet. Here, we report an efficient, autonomous solar water-splitting device based on a gold nanorod array in which essentially all charge carriers involved in the oxidation and reduction steps arise from the hot electrons resulting from the excitation of surface plasmons in the nanostructured gold. Each nanorod functions without external wiring, producing 5 × 10(13) H₂ molecules per cm(2) per s under 1 sun illumination (AM 1.5 and 100 mW cm(-2)), with unprecedented long-term operational stability.

Reduction mechanisms of additives on Si anodes of Li-ion batteries.

PubMed

Martínez de la Hoz, Julibeth M; Balbuena, Perla B

2014-08-28

Solid-electrolyte interphase (SEI) layers are films deposited on the surface of Li-ion battery electrodes during battery charge and discharge processes. They are due to electrochemical instability of the electrolyte which causes electron transfer from (to) the anode (cathode) surfaces. The films could have a protective passivating role and therefore understanding the detailed reduction (oxidation) processes is essential. Here density functional theory and ab initio molecular dynamics simulations are used to investigate the reduction mechanisms of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) on lithiated silicon surfaces. These species are frequently used as "additives" to improve the SEI properties. It is found that on lithiated Si anodes (with low to intermediate degrees of lithiation) VC may be reduced via a 2e(-) mechanism yielding an opened VC(2-) anion. At higher degrees of lithiation, such a species receives two extra electrons from the surface resulting in an adsorbed CO(2-)(ads) anion and a radical anion ˙OC2H2O(2-). Additionally, in agreement with experimental observations, it is shown that CO2 can be generated from reaction of VC with the CO3(2-)anion, a product of the reduction of the main solvent, ethylene carbonate (EC). On the other hand, FEC reduction on LixSiy surfaces is found to be independent of the degree of lithiation, and occurs through three mechanisms. One of them leads to an adsorbed VC(2-) anion upon release from the FEC molecule and adsorption on the surface of F(-) and one H atom. Thus in some cases, the reduction of FEC may lead to the exact same reduction products as that of VC, which explains similarities in SEI layers formed in the presence of these additives. However, FEC may be reduced via two other multi-electron transfer mechanisms that result in formation of either CO2(2-), F(-), and ˙CH2CHO(-) or CO(2-), F(-), and ˙OCH2CHO(-). These alternative reduction products may oligomerize and form SEI layers with different components than those formed in the presence of VC. In all cases, FEC reduction also leads to formation of LiF moieties on the anode surface, in agreement with reported experimental data. The crucial role of the surface in each of these mechanisms is thoroughly explained.

Observation of self-excited acoustic vortices in defect-mediated dust acoustic wave turbulence.

PubMed

Tsai, Ya-Yi; I, Lin

2014-07-01

Using the self-excited dust acoustic wave as a platform, we demonstrate experimental observation of self-excited fluctuating acoustic vortex pairs with ± 1 topological charges through spontaneous waveform undulation in defect-mediated turbulence for three-dimensional traveling nonlinear longitudinal waves. The acoustic vortex pair has helical waveforms with opposite chirality around the low-density hole filament pair in xyt space (the xy plane is the plane normal to the wave propagation direction). It is generated through ruptures of sequential crest surfaces and reconnections with their trailing ruptured crest surfaces. The initial rupture is originated from the amplitude reduction induced by the formation of the kinked wave crest strip with strong stretching through the undulation instability. Increasing rupture causes the separation of the acoustic vortex pair after generation. A similar reverse process is followed for the acoustic vortex annihilating with the opposite-charged acoustic vortex from the same or another pair generation.

Surface field theories of point group symmetry protected topological phases

NASA Astrophysics Data System (ADS)

Huang, Sheng-Jie; Hermele, Michael

2018-02-01

We identify field theories that describe the surfaces of three-dimensional bosonic point group symmetry protected topological (pgSPT) phases. The anomalous nature of the surface field theories is revealed via a dimensional reduction argument. Specifically, we study three different surface field theories. The first field theory is quantum electrodynamics in three space-time dimensions (QED3) with four flavors of fermions. We show this theory can describe the surfaces of a majority of bosonic pgSPT phases protected by a single mirror reflection, or by Cn v point group symmetry for n =2 ,3 ,4 ,6 . The second field theory is a variant of QED3 with charge-1 and charge-3 Dirac fermions. This field theory can describe the surface of a reflection symmetric pgSPT phase built by placing an E8 state on the mirror plane. The third field theory is an O (4 ) nonlinear sigma model with a topological theta term at θ =π , or, equivalently, a noncompact CP1 model. Using a coupled wire construction, we show this is a surface theory for bosonic pgSPT phases with U (1 ) ×Z2P symmetry. For the latter two field theories, we discuss the connection to gapped surfaces with topological order. Moreover, we conjecture that the latter two field theories can describe surfaces of more general bosonic pgSPT phases with Cn v point group symmetry.

Toxicity of silver nanoparticles towards tumoral human cell lines U-937 and HL-60.

PubMed

Barbasz, Anna; Oćwieja, Magdalena; Roman, Maciej

2017-08-01

The toxicity of three types of silver nanoparticles towards histiocytic lymphoma (U-937) and human promyelocytic cells (HL-60) was studied. The nanoparticles were synthesized in a chemical reduction method using sodium borohydride. Trisodium citrate and cysteamine hydrochloride were used to generate a negative and positive nanoparticle surface charge. The evaluation of cell viability, membrane integrity, antioxidant activity and the induction of inflammation were used to evaluate the difference in cellular response to the nanoparticle treatment. The results revealed that the cysteamine-stabilized (positively charged) nanoparticles (SBATE) were the least toxic although they exhibited a similar ion release profile as the unmodified (negatively charged) nanoparticles obtained using sodium borohydride (SBNM). Citrate-stabilized nanoparticles (SBTC) induced superoxide dismutase (SOD) activity in the HL-60 cells and total antioxidant activity in the U-937 cells despite their resistance to oxidative dissolution. The toxicity of SBNM nanoparticles was manifested in the disruption of membrane integrity, decrease in the mitochondrial functions of cells and the induction of inflammation. These findings allowed to conclude that mechanism of silver nanoparticle cytotoxicity is the combination of effects coming from the surface charge of nanoparticles, released silver ions and biological activity of stabilizing agent molecules. Copyright © 2017 Elsevier B.V. All rights reserved.

The Functionality of Surface Hydroxy Groups on the Selectivity and Activity of Carbon Dioxide Reduction over Cuprous Oxide in Aqueous Solutions.

PubMed

Yang, Piaoping; Zhao, Zhi-Jian; Chang, Xiaoxia; Mu, Rentao; Zha, Shenjun; Zhang, Gong; Gong, Jinlong

2018-06-25

Carbon dioxide (CO 2 ) reduction in aqueous solutions is an attractive strategy for carbon capture and utilization. Cuprous oxide (Cu 2 O) is a promising catalyst for CO 2 reduction as it can convert CO 2 into valuable hydrocarbons and suppress the side hydrogen evolution reaction (HER). However, the nature of the active sites in Cu 2 O remains under debate because of the complex surface structure of Cu 2 O under reducing conditions, leading to limited guidance in designing improved Cu 2 O catalysts. This paper describes the functionality of surface-bonded hydroxy groups on partially reduced Cu 2 O(111) for the CO 2 reduction reaction (CO 2 RR) by combined density functional theory (DFT) calculations and experimental studies. We find that the surface hydroxy groups play a crucial role in the CO 2 RR and HER, and a moderate coverage of hydroxy groups is optimal for promotion of the CO 2 RR and suppression of the HER simultaneously. Electronic structure analysis indicates that the charge transfer from hydroxy groups to coordination-unsaturated Cu (Cu CUS ) sites stabilizes surface-adsorbed COOH*, which is a key intermediate during the CO 2 RR. Moreover, the CO 2 RR was evaluated over Cu 2 O octahedral catalysts with {111} facets and different surface coverages of hydroxy groups, which demonstrates that Cu 2 O octahedra with moderate coverage of hydroxy groups can indeed enhance the CO 2 RR and suppress the HER. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic application of antimicrobial sprays to sanitize food handling and processing surfaces for enhanced food safety

NASA Astrophysics Data System (ADS)

Lyons, Shawn M.; Harrison, Mark A.; Law, S. Edward

2011-06-01

Human illnesses and deaths caused by foodborne pathogens (e.g., Salmonella enterica, Listeria monocytogenes, Escherichia coli O157:H7, etc.) are of increasing concern globally in maintaining safe food supplies. At various stages of the food production, processing and supply chain antimicrobial agents are required to sanitize contact surfaces. Additionally, during outbreaks of contagious pathogenic microorganisms (e.g., H1N1 influenza), public health requires timely decontamination of extensive surfaces within public schools, mass transit systems, etc. Prior publications verify effectiveness of air-assisted, induction-charged (AAIC) electrostatic spraying of various chemical and biological agents to protect on-farm production of food crops...typically doubling droplet deposition efficiency with concomitant increases in biological control efficacy. Within a biosafety facility this present work evaluated the AAIC electrostatic-spraying process for application of antimicrobial liquids onto various pathogen-inoculated food processing and handling surfaces as a food safety intervention strategy. Fluoroanalysis of AAIC electrostatic sprays (-7.2 mC/kg charge-to-mass ratio) showed significantly greater (p<0.05) mass of tracer active ingredient (A.I.) deposited onto target surfaces at various orientations as compared both to a similar uncharged spray nozzle (0 mC/kg) and to a conventional hydraulic-atomizing nozzle. Per unit mass of A.I. dispensed toward targets, for example, A.I. mass deposited by AAIC electrostatic sprays onto difficult to coat backsides was 6.1-times greater than for similar uncharged sprays and 29.0-times greater than for conventional hydraulic-nozzle sprays. Even at the 56% reduction in peracetic acid sanitizer A.I. dispensed by AAIC electrostatic spray applications, they achieved equal or greater CFU population reductions of Salmonella on most target orientations and materials as compared to uncharged sprays and conventional full-rate hydraulic-nozzle sprays.

Enhanced photocatalytic performance of KNbO3(100)/reduced graphene oxide nanocomposites investigated using first-principles calculations: RGO reductivity effect

NASA Astrophysics Data System (ADS)

Zhang, Pan; Shen, Yanqing; Wu, Wenjing; Li, Jun; Zhou, Zhongxiang

2018-03-01

Although a number of various reduced graphene oxide (RGO)-based nanomaterials with enhanced photocatalytic performance have recently been characterized, the effect of RGO reductivity on their performance is still not clear. Herein, KNbO3(100) surface modification with three RGO sheets of different reductivity is investigated using first-principles calculations, revealing that increasing RGO reductivity enhances the photocatalytic performance of KNbO3(100)/RGO nanocomposites. In contrast to CeO2/RGO nanocomposites, the O atoms of RGO inhibit the photoactivity of KNbO3/RGO nanocomposites by restraining the effect of inducing a red shift of the corresponding photocatalytic absorption spectra by C 2p states. Increased RGO reductivity extends its absorption edge to the visible light region of the optical absorption and also promotes charge transfer from the KNbO3(100) surface to RGO sheets, in contrast to the behavior observed for g-C3N4/RGO composites. Overall, this work provides a reasonable explanation of controversial experimental results obtained previously, paving the way to the development of highly efficient RGO-based photocatalysts and promoting further photocatalytic applications of KNbO3/RGO nanocomposites.

Novel mesoporous MnCo2O4 nanorods as oxygen reduction catalyst at neutral pH in microbial fuel cells.

PubMed

Kumar, Ravinder; Singh, Lakhveer; Wahid, Zularisam Ab; Mahapatra, Durga Madhab; Liu, Hong

2018-04-01

The aim of this work was to evaluate the comparative performance of hybrid metal oxide nanorods i.e. MnCo 2 O 4 nanorods (MCON) and single metal oxide nanorods i.e. Co 3 O 4 nanorods (CON) as oxygen reduction catalyst in microbial fuel cells (MFC). Compared to the single metal oxide, the hybrid MCON exhibited a higher BET surface area and provided additional positively charged ions, i.e., Co 2+ /Co 3+ and Mn 3+ /Mn 4+ on its surfaces, which increased the electro-conductivity of the cathode and improved the oxygen reduction kinetics significantly, achieved an i o of 6.01 A/m 2 that was 12.4% higher than CON. Moreover, the porous architecture of MCON facilitated the diffusion of electrolyte, reactants and electrons during the oxygen reduction, suggested by lower diffusion (R d ), activation (R act ) and ohmic resistance (R ohm ) values. This enhanced oxygen reduction by MCON boosted the power generation in MFC, achieving a maximum power density of 587 mW/m 2 that was ∼29% higher than CON. Published by Elsevier Ltd.

Mechanisms of metal sorption by biochars: Biochar characteristics and modifications.

PubMed

Li, Hongbo; Dong, Xiaoling; da Silva, Evandro B; de Oliveira, Letuzia M; Chen, Yanshan; Ma, Lena Q

2017-07-01

Biochar produced by thermal decomposition of biomass under oxygen-limited conditions has received increasing attention as a cost-effective sorbent to treat metal-contaminated waters. However, there is a lack of information on the roles of different sorption mechanisms for different metals and recent development of biochar modification to enhance metal sorption capacity, which is critical for biochar field application. This review summarizes the characteristics of biochar (e.g., surface area, porosity, pH, surface charge, functional groups, and mineral components) and main mechanisms governing sorption of As, Cr, Cd, Pb, and Hg by biochar. Biochar properties vary considerably with feedstock material and pyrolysis temperature, with high temperature producing biochars with higher surface area, porosity, pH, and mineral contents, but less functional groups. Different mechanisms dominate sorption of As (complexation and electrostatic interactions), Cr (electrostatic interactions, reduction, and complexation), Cd and Pb (complexation, cation exchange, and precipitation), and Hg (complexation and reduction). Besides sorption mechanisms, recent advance in modifying biochar by loading with minerals, reductants, organic functional groups, and nanoparticles, and activation with alkali solution to enhance metal sorption capacity is discussed. Future research needs for field application of biochar include competitive sorption mechanisms of co-existing metals, biochar reuse, and cost reduction of biochar production. Published by Elsevier Ltd.

Modeling of the oxygen reduction reaction for dense LSM thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Tao; Liu, Jian; Yu, Yang

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Modeling of the oxygen reduction reaction for dense LSM thin films

DOE PAGES

Yang, Tao; Liu, Jian; Yu, Yang; ...

2017-10-17

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Pulsed laser deposited metal oxide thin films mediated controlled adsorption of proteins

NASA Astrophysics Data System (ADS)

Kim, Se Jin

Several metal oxide thin films were grown on Si substrate by pulsed laser deposition for controlling adsorption of proteins. No intentional heating of substrate and introduction of oxygen gas during growth were employed. Additionally, fibrinogen, bovine serum albumin (BSA), and lysozyme were used as model protein in this study. The film properties such as cyratllinity, surface roughness, surface electrical charge and chemistry were investigated by many techniques in order to obtain the relationship with protein adsorption. Firstly, as grown Ta2O5 and ZnO thin film were used to study the effects of surface charge on the behaviors of BSA and lysozyme adsorption. The protein thickness results by ellipsometry showed that negatively charged Ta2O5 had a stronger affinity to positively charged lysozyme, while positively charged ZnO had a stronger affinity to negatively charged BSA. The results confirmed electrostatic interaction due to surface charge is one of main factors for determining adsorption of proteins. Furthermore, annealing studies were performed by heat treatment of as grown Ta2O5 and ZnO at 800°C in air ambience. Annealed Ta2O5 thin film had almost wetting property (from 10.02° to less than 1˜2°) and the change of cystallinity (from amorphous to cyrsalline) while annealed ZnO thin film had a reduced contact angle (from 75.65° to 39.41°) and remained to crystalline structure. The fibrinogen thickness on annealed Ta2O5 film was increased compared with as grown sample, while heat treated ZnO film showed much reduction of fibrinogen adsorption. Binary Ta-Zn oxide thin films (TZ) were grown by preparing PLD target composed of 50 wt% Ta2O5 and 50 wt% ZnO. This binary film had IEP pH 7.1 indicating nearly neutral charge in pH 7.4 PBS solution, and hydrophilic property. Ellipsometrical results showed that TZ film had the lowest fibrinogen, BSA and lysozyme thickness after 120 min adsorption compared with Ta2O5 and ZnO. Other samples, bilayer oxide films in which Ta2O5 and ZnO coexist were also employed to study adsorption behaviors. Especially, Ta2O 5-based bilayer films revealed zero adsorption of lysozyme.

Enhanced photocatalytic CO₂-reduction activity of electrospun mesoporous TiO₂ nanofibers by solvothermal treatment.

PubMed

Fu, Junwei; Cao, Shaowen; Yu, Jiaguo; Low, Jingxiang; Lei, Yongpeng

2014-06-28

Photocatalytic reduction of CO2 into renewable hydrocarbon fuels using semiconductor photocatalysts is considered as a potential solution to the energy deficiency and greenhouse effect. In this work, mesoporous TiO2 nanofibers with high specific surface areas and abundant surface hydroxyl groups are prepared using an electrospinning strategy combined with a subsequent calcination process, followed by a solvothermal treatment. The solvothermally treated mesoporous TiO2 nanofibers exhibit excellent photocatalytic performance on CO2 reduction into hydrocarbon fuels. The significantly improved photocatalytic activity can be attributed to the enhanced CO2 adsorption capacity and the improved charge separation after solvothermal treatment. The highest activity is achieved for the sample with a 2-h solvothermal treatment, showing 6- and 25-fold higher CH4 production rate than those of TiO2 nanofibers without solvothermal treatment and P25, respectively. This work may also provide a prototype for studying the effect of solvothermal treatment on the structure and photocatalytic activity of semiconductor photocatalysts.

An equivalent body surface charge model representing three-dimensional bioelectrical activity

NASA Technical Reports Server (NTRS)

He, B.; Chernyak, Y. B.; Cohen, R. J.

1995-01-01

A new surface-source model has been developed to account for the bioelectrical potential on the body surface. A single-layer surface-charge model on the body surface has been developed to equivalently represent bioelectrical sources inside the body. The boundary conditions on the body surface are discussed in relation to the surface-charge in a half-space conductive medium. The equivalent body surface-charge is shown to be proportional to the normal component of the electric field on the body surface just outside the body. The spatial resolution of the equivalent surface-charge distribution appears intermediate between those of the body surface potential distribution and the body surface Laplacian distribution. An analytic relationship between the equivalent surface-charge and the surface Laplacian of the potential was found for a half-space conductive medium. The effects of finite spatial sampling and noise on the reconstruction of the equivalent surface-charge were evaluated by computer simulations. It was found through computer simulations that the reconstruction of the equivalent body surface-charge from the body surface Laplacian distribution is very stable against noise and finite spatial sampling. The present results suggest that the equivalent body surface-charge model may provide an additional insight to our understanding of bioelectric phenomena.

Probing Ultrafast Electron Dynamics at Surfaces Using Soft X-Ray Transient Reflectivity Spectroscopy

NASA Astrophysics Data System (ADS)

Baker, L. Robert; Husek, Jakub; Biswas, Somnath; Cirri, Anthony

The ability to probe electron dynamics with surface sensitivity on the ultrafast time scale is critical for understanding processes such as charge separation, injection, and surface trapping that mediate efficiency in catalytic and energy conversion materials. Toward this goal, we have developed a high harmonic generation (HHG) light source for femtosecond soft x-ray reflectivity. Using this light source we investigated the ultrafast carrier dynamics at the surface of single crystalline α-Fe2O3, polycrystalline α-Fe2O3, and the mixed metal oxide, CuFeO2. We have recently demonstrated that CuFeO2 in particular is a selective catalyst for photo-electrochemical CO2 reduction to acetate; however, the role of electronic structure and charge carrier dynamics in mediating catalytic selectivity has not been well understood. Soft x-ray reflectivity measurements probe the M2,3, edges of the 3d transition metals, which provide oxidation and spin state resolution with element specificity. In addition to chemical state specificity, these measurements are also surface sensitive, and by independently simulating the contributions of the real and imaginary components of the complex refractive index, we can differentiate between surface and sub-surface contributions to the excited state spectrum. Accordingly, this work demonstrates the ability to probe ultrafast carrier dynamics in catalytic materials with element and chemical state specificity and with surface sensitivity.

Carbothermic reduction of uranium oxides into solvent metallic baths

NASA Astrophysics Data System (ADS)

Guisard Restivo, Thomaz A.; Capocchi, José D. T.

2004-09-01

The carbothermic reduction of UO 2 and U 3O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3O 8 charges, respectively. One example for another system containing Al 2O 3 is also shown.

First principles investigation of heterogeneous catalysis on metal oxide surfaces

NASA Astrophysics Data System (ADS)

Ghoussoub, Mireille

Metal oxides possess unique electronic and structural properties that render them highly favourable for applications in heterogeneous catalysis. In this study, computational atomistic modelling based on Density Functional Theory was used to investigate the reduction of carbon dioxide over hydroxylated indium oxide nanoparticles, as well at the activation of methane over oxygen-covered bimetallic surfaces. The first study employed metadynamics-biased ab initio molecular dynamics to obtain the free energy surface of the various reaction steps at finite temperature. In the second study, the nudged elastic band method was used to probe the C-H activation mechanisms for different surface configurations. In both cases, activation energies, reaction energies, transition state structures, and charge analysis results are used to explain the underlying mechanistic pathways.

Upregulation of BMSCs Osteogenesis by Positively-Charged Tertiary Amines on Polymeric Implants via Charge/iNOS Signaling Pathway

PubMed Central

Zhang, Wei; Liu, Na; Shi, Haigang; Liu, Jun; Shi, Lianxin; Zhang, Bo; Wang, Huaiyu; Ji, Junhui; Chu, Paul K.

2015-01-01

Positively-charged surfaces on implants have a similar potential to upregulate osteogenesis of bone marrow-derived mesenchymal stem cells (BMSCs) as electromagnetic therapy approved for bone regeneration. Generally, their osteogenesis functions are generally considered to stem from the charge-induced adhesion of extracellular matrix (ECM) proteins without exploring the underlying surface charge/cell signaling molecule pathways. Herein, a positively-charged surface with controllable tertiary amines is produced on a polymer implant by plasma surface modification. In addition to inhibiting the TNF-α expression, the positively-charged surface with tertiary amines exhibits excellent cytocompatibility as well as remarkably upregulated osteogenesis-related gene/protein expressions and calcification of the contacted BMSCs. Stimulated by the charged surface, these BMSCs display high iNOS expressions among the three NOS isoforms. Meanwhile, downregulation of the iNOS by L-Can or siRNA inhibit osteogenic differentiation in the BMSCs. These findings suggest that a positively-charged surface with tertiary amines induces osteogenesis of BMSCs via the surface charge/iNOS signaling pathway in addition to elevated ECM protein adhesion. Therefore, creating a positively-charged surface with tertiary amines is a promising approach to promote osseointegration with bone tissues. PMID:25791957

Persistent Charge-Density-Wave Order in Single-Layer TaSe2.

PubMed

Ryu, Hyejin; Chen, Yi; Kim, Heejung; Tsai, Hsin-Zon; Tang, Shujie; Jiang, Juan; Liou, Franklin; Kahn, Salman; Jia, Caihong; Omrani, Arash A; Shim, Ji Hoon; Hussain, Zahid; Shen, Zhi-Xun; Kim, Kyoo; Min, Byung Il; Hwang, Choongyu; Crommie, Michael F; Mo, Sung-Kwan

2018-02-14

We present the electronic characterization of single-layer 1H-TaSe 2 grown by molecular beam epitaxy using a combined angle-resolved photoemission spectroscopy, scanning tunneling microscopy/spectroscopy, and density functional theory calculations. We demonstrate that 3 × 3 charge-density-wave (CDW) order persists despite distinct changes in the low energy electronic structure highlighted by the reduction in the number of bands crossing the Fermi energy and the corresponding modification of Fermi surface topology. Enhanced spin-orbit coupling and lattice distortion in the single-layer play a crucial role in the formation of CDW order. Our findings provide a deeper understanding of the nature of CDW order in the two-dimensional limit.

Studies of oxidation and thermal reduction of the Cu(100) surface using a slow positron beam

NASA Astrophysics Data System (ADS)

Maddox, W. B.; Fazleev, N. G.; Nadesalingam, M. P.; Weiss, A. H.

2007-10-01

Positron probes of surfaces of oxides that play a fundamental role in modern science and technology are capable to non-destructively provide information that is both unique to the probe and complimentary to that extracted using other more standard techniques. We discuss recent progress in studies of oxidation and thermal reduction of the Cu(100) surface using positron-annihilation-induced Auger-electron spectroscopy (PAES). PAES measurements show a large increase in the intensity of the Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 C. The intensity then decreases monotonically as the annealing temperature is increased to 600 C. Experimental PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and surface reconstruction. The effects of oxygen adsorption and defects on localization of the positron surface state wave function and positron annihilation characteristics are also analyzed. Possible explanations are provided for the observed behavior of the intensity of the positron annihilation induced Cu M2,3VV Auger peak with changes of the annealing temperature.

Unraveling the Agglomeration Mechanism in Charged Block Copolymer and Surfactant Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.

Here, we report a molecular dynamics simulation investigation of self-assembly and complex formation of charged-neutral double hydrophilic and hydrophobic-hydrophilic block copolymers (BCP) with oppositely charged surfactants. Furthermore, the structure of the surfactant micelles and the BCP aggregation on the micelle surface is systematically studied for five different BCP volume fractions that also mimics a reduction of the surfactant concentration. The local electrostatic interactions between the oppositely charged species encourage the formation of core-shell structures between the surfactant micelles where the surfactants form the cores and the charged blocks of the BCP form the corona. The emergent morphologies of these aggregatesmore » are contingent upon the nature of the BCP neutral blocks. The hydrophilic neutral blocks agglomerate with the micelles as hairy colloidal structures while the hydrophobic neutrals agglomerate in lamellar structures with the surfactant micelles. The distribution of counterion charges along the simulation box show a close-to-normal density distribution for the hydrophilic neutral blocks and a binodal distribution for hydrophobic neutral blocks. No specific surfactant concentration dependent scaling relation is observed as opposed to the simpler case of homo-polyelectrolytes.« less

Unraveling the Agglomeration Mechanism in Charged Block Copolymer and Surfactant Complexes

DOE PAGES

Borreguero, Jose M.; Pincus, Philip A.; Sumpter, Bobby G.; ...

2017-01-27

Here, we report a molecular dynamics simulation investigation of self-assembly and complex formation of charged-neutral double hydrophilic and hydrophobic-hydrophilic block copolymers (BCP) with oppositely charged surfactants. Furthermore, the structure of the surfactant micelles and the BCP aggregation on the micelle surface is systematically studied for five different BCP volume fractions that also mimics a reduction of the surfactant concentration. The local electrostatic interactions between the oppositely charged species encourage the formation of core-shell structures between the surfactant micelles where the surfactants form the cores and the charged blocks of the BCP form the corona. The emergent morphologies of these aggregatesmore » are contingent upon the nature of the BCP neutral blocks. The hydrophilic neutral blocks agglomerate with the micelles as hairy colloidal structures while the hydrophobic neutrals agglomerate in lamellar structures with the surfactant micelles. The distribution of counterion charges along the simulation box show a close-to-normal density distribution for the hydrophilic neutral blocks and a binodal distribution for hydrophobic neutral blocks. No specific surfactant concentration dependent scaling relation is observed as opposed to the simpler case of homo-polyelectrolytes.« less

Charging of dust grains in a plasma with negative ions

NASA Astrophysics Data System (ADS)

Kim, Su-Hyun; Merlino, Robert L.

2006-05-01

The effect of negative ions on the charging of dust particles in a plasma is investigated experimentally. A plasma containing a very low percentage of electrons is formed in a single-ended SF6 is admitted into the vacuum system. The relatively cold (Te≈0.2eV ) readily attach to SF6 molecules to form SF6- negative ions. Calculations of the dust charge indicate that for electrons, negative ions, and positive ions of comparable temperatures, the charge (or surface potential) of the dust can be positive if the positive ion mass is smaller than the negative ion mass and if ɛ, the ratio of the electron to positive ion density, is sufficiently small. The K+ positive ions (mass 39amu) and SF6- negative ions (mass 146amu), and also utilizes a rotating cylinder to dispense dust into the plasma column. Analysis of the current-voltage characteristics of a Langmuir probe in the dusty plasma shows evidence for the reduction in the (magnitude) of the negative dust charge and the transition to positively charged dust as the relative concentration of the residual electrons is reduced. Some remarks are offered concerning experiments that could become possible in a dusty plasma with positive grains.

Sustainable agriculture and nitrogen reduction: an open field experiment using natural zeolitites in silty-clay reclaimed soil at Codigoro (Po River Delta, Ferrara, Italy)

NASA Astrophysics Data System (ADS)

Faccini, Barbara; Di Giuseppe, Dario; Mastrocicco, Micòl; Coltorti, Massimo; Colombani, Nicolò; Ferretti, Giacomo

2014-05-01

Following the guidelines of Nitrate and Water Framework Directives (91/676/CEE, 200/60/CE) an innovative integrated zeolitite cycle is being tested on a reclaimed clayey-silt soil in the Po Delta area (Ferrara Province, Italy), in the framework of the EU-funded ZeoLIFE project (LIFE+10 ENV/IT/000321). Natural zeolitites are pyroclastic rocks containing more than 50% of zeolites, a kind of hydrous minerals with peculiar physical and chemical properties, like high and selective cation exchange capacity (CEC), molecular adsorption and reversible dehydration. Zeolitites can trap NH4+ from solutions and release it gradually to the plant roots once they have been mixed in agricultural soils, allowing both fertilization and irrigation reduction and improvement of the yield. The fertilization reduction can result in a decrease of the nitrate content in groundwater and surface waters, ultimately leading to a mitigation of nutrient excess in the environment. Similarly, reduction of irrigation water means a minor exploitation of the water resource. The selected material used in the project is a chabazite zeolitite coming from a quarry near Sorano in Central Italy (Bolsena volcanic district). The open-field experimentation foresees two year of cultivation. A surface of about 6 ha has been divided into six parcels: three control parcels are cultivated and irrigated in traditional way; two parcels have been added with coarse-grained (ø = 3- 6 mm) natural zeolitite at different zeolitite/soil ratios (5 kg/m2 and 15 kg/m2) and one has been mixed with fine-grained (ø < 3 mm) NH4+-charged zeolitite at 10 kg/m2. Zeolitite/soil ratios have been determined upon a series of greenhouse tests, and the ammonium enriched material is obtained by cation exchange with swine manure in a specifically conceived prototype. The environmental quality of soil and water in each parcel is monitored by periodic soil, groundwater and porewater analyses. Soil EC, temperature and volumetric water content are continuously measured with probes at different depth (5-30-50-100-150 cm). The quality of surface water is checked by analyzing the outflow from the drains of the sub-irrigation system installed in the field. An automated meteorological station has been also installed in order to quantify rainfalls and sun irradiation for water balance calculation. During the first year, a no-food variety of sorghum has been cultivated. In the parcels treated with natural zeolitite and in that bearing NH4+-charged zeolitite, the fertilization has been reduced by 30% and 50% with respect to the controls. Notwithstanding these reductions, the yield increased by 5% and 15% in the parcel added with natural zeolitite and in that treated with NH4+-charged zeolitite, respectively. As confirmed by previously performed laboratory leaching tests, NH4+ in porewater and surface water was comparable in all parcels (

Modulation of protein stability and aggregation properties by surface charge engineering.

PubMed

Raghunathan, Govindan; Sokalingam, Sriram; Soundrarajan, Nagasundarapandian; Madan, Bharat; Munussami, Ganapathiraman; Lee, Sun-Gu

2013-09-01

An attempt to alter protein surface charges through traditional protein engineering approaches often affects the native protein structure significantly and induces misfolding. This limitation is a major hindrance in modulating protein properties through surface charge variations. In this study, as a strategy to overcome such a limitation, we attempted to co-introduce stabilizing mutations that can neutralize the destabilizing effect of protein surface charge variation. Two sets of rational mutations were designed; one to increase the number of surface charged amino acids and the other to decrease the number of surface charged amino acids by mutating surface polar uncharged amino acids and charged amino acids, respectively. These two sets of mutations were introduced into Green Fluorescent Protein (GFP) together with or without stabilizing mutations. The co-introduction of stabilizing mutations along with mutations for surface charge modification allowed us to obtain functionally active protein variants (s-GFP(+15-17) and s-GFP(+5-6)). When the protein properties such as fluorescent activity, folding rate and kinetic stability were assessed, we found the possibility that the protein stability can be modulated independently of activity and folding by engineering protein surface charges. The aggregation properties of GFP could also be altered through the surface charge engineering.

Photoelectrochemical electrodes

NASA Technical Reports Server (NTRS)

Williams, R. M.; Rembaum, A. (Inventor)

1983-01-01

The surface of a moderate band gap semiconductor such as p-type molybdenum sulfide is modified to contain an adherent film of charge mediating ionene polymer containing an electroactive unit such as bipyridimium. Electron transport between the electrode and the mediator film is favorable and photocorrosion and recombination processes are suppressed. Incorporation of particles of catalyst such as platinum within the film provides a reduction in overvoltage. The polymer film is readily deposited on the electrode surface and can be rendered stable by ionic or addition crosslinking. Catalyst can be predispersed in the polymer film or a salt can be impregnated into the film and reduced therein.

Molecular simulation study of feruloyl esterase adsorption on charged surfaces: effects of surface charge density and ionic strength.

PubMed

Liu, Jie; Peng, Chunwang; Yu, Gaobo; Zhou, Jian

2015-10-06

The surrounding conditions, such as surface charge density and ionic strength, play an important role in enzyme adsorption. The adsorption of a nonmodular type-A feruloyl esterase from Aspergillus niger (AnFaeA) on charged surfaces was investigated by parallel tempering Monte Carlo (PTMC) and all-atom molecular dynamics (AAMD) simulations at different surface charge densities (±0.05 and ±0.16 C·m(-2)) and ionic strengths (0.007 and 0.154 M). The adsorption energy, orientation, and conformational changes were analyzed. Simulation results show that whether AnFaeA can adsorb onto a charged surface is mainly controlled by electrostatic interactions between AnFaeA and the charged surface. The electrostatic interactions between AnFaeA and charged surfaces are weakened when the ionic strength increases. The positively charged surface at low surface charge density and high ionic strength conditions can maximize the utilization of the immobilized AnFaeA. The counterion layer plays a key role in the adsorption of AnFaeA on the negatively charged COOH-SAM. The native conformation of AnFaeA is well preserved under all of these conditions. The results of this work can be used for the controlled immobilization of AnFaeA.

The active surface of suspended particles as a predictor of lung function and pulmonary symptoms in Austrian school children

NASA Astrophysics Data System (ADS)

Moshammer, Hanns; Neuberger, Manfred

At a central elementary school in the capital of Upper Austria children aged 7-10 years underwent repeated respiratory health checkups (questionnaires, diaries, spirometry). Between March and May 2001 the daily means of the signals of a diffusion charging sensor, measuring the "active surface" of suspended particles, and a photoelectric aerosol sensor, measuring the particle-bound polycyclic aromatic hydrocarbons, were related to spirometric results of the total 164 children examined and to the daily symptom scores of a susceptible subgroup. Significant reductions of forced vital capacity ( p=0.006) and forced expiratory volume in the first second ( p=0.001) and significant increases of wheezing ( p=0.001), shortness of breath ( p=0.041), cough in the evening ( p=0.031) and at night ( p=0.018) were found with increase of "active surface" of suspended particles measured at the adjacent outdoor monitoring station, but not with the increase of particle-bound polycyclic aromatic hydrocarbons. Monitoring "active surface" of particles with diameters of about 10 nm-1 μm by means of a diffusion charging sensor might provide additional information in surveillance of particulate matter for prevention of acute effects on respiratory health.

Effect of nano-scale morphology on micro-channel wall surface and electrical characterization in lead silicate glass micro-channel plate

NASA Astrophysics Data System (ADS)

Cai, Hua; Li, Fangjun; Xu, Yanglei; Bo, Tiezhu; Zhou, Dongzhan; Lian, Jiao; Li, Qing; Cao, Zhenbo; Xu, Tao; Wang, Caili; Liu, Hui; Li, Guoen; Jia, Jinsheng

2017-10-01

Micro-channel plate (MCP) is a two dimensional arrays of microscopic channel charge particle multiplier. Silicate composition and hydrogen reduction are keys to determine surface morphology of micro-channel wall in MCP. In this paper, lead silicate glass micro-channel plates in two different cesium contents (0at%, 0.5at%) and two different hydrogen reduction temperatures (400°C,450°C) were present. The nano-scale morphology, elements content and chemical states of microporous wall surface treated under different alkaline compositions and reduction conditions was investigated by Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS), respectively. Meanwhile, the electrical characterizations of MCP, including the bulk resistance, electron gain and the density of dark current, were measured in a Vacuum Photoelectron Imaging Test Facility (VPIT).The results indicated that the granular phase occurred on the surface of microporous wall and diffuses in bulk glass is an aggregate of Pb atom derived from the reduction of Pb2+. In micro-channel plate, the electron gain and bulk resistance were mainly correlated to particle size and distribution, the density of dark current (DDC) went up with the increasing root-mean-square roughness (RMS) on the microporous wall surface. Adding cesiums improved the size of Pb atomic aggregation, lowered the relative concentration of [Pb] reduced from Pb2+ and decreased the total roughness of micro-channel wall surface, leading a higher bulk resistance, a lower electron gain and a less dark current. Increasing hydrogen reduction temperature also improved the size of Pb atomic aggregation, but enhanced the relative concentration of [Pb] and enlarged the total roughness of micro-channel wall surface, leading a higher bulk resistance, a lower electron gain and a larger dark current. The reasons for the difference of electrical characteristics were discussed.

Adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface: A spectroscopic study

NASA Astrophysics Data System (ADS)

Lucilha, Adriana Campano; Bonancêa, Carlos Eduardo; Barreto, Wagner José; Takashima, Keiko

2010-01-01

The adsorption of the diazo dye Direct Red 23 onto a zinc oxide surface at 30 °C in the dark was investigated. The color reduction was monitored by spectrophotometry at 503 nm. The FTIR and Raman spectra of the Direct Red 23 adsorption as a function of ZnO concentration were registered. From the PM3 semi-empirical calculations of the atomic charge density and dipole moment of the Direct Red 23 molecule, it was demonstrated that the azo dye molecule may be adsorbed onto the ZnO surface through molecule geometry modifications, enhancing the interfacial area causing a variation in the bonding frequencies.

Strong influence of coadsorbate interaction on CO desorption dynamics on Ru(0001) probed by ultrafast x-ray spectroscopy and ab initio simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xin, H.; LaRue, J.; Oberg, H.

2015-04-16

We show that coadsorbed oxygen atoms have a dramatic influence on the CO desorption dynamics from Ru(0001). In contrast to the precursor-mediated desorption mechanism on Ru(0001), the presence of surface oxygen modifies the electronic structure of Ru atoms such that CO desorption occurs predominantly via the direct pathway. This phenomenon is directly observed in an ultrafast pump-probe experiment using a soft x-ray free-electron laser to monitor the dynamic evolution of the valence electronic structure of the surface species. This is supported with the potential of mean force along the CO desorption path obtained from density-functional theory calculations. Charge density distributionmore » and frozen-orbital analysis suggest that the oxygen-induced reduction of the Pauli repulsion, and consequent increase of the dative interaction between the CO 5σ and the charged Ru atom, is the electronic origin of the distinct desorption dynamics. Ab initio molecular dynamics simulations of CO desorption from Ru(0001) and oxygen-coadsorbed Ru(0001) provide further insights into the surface bond-breaking process.« less

Voltammetric studies of hemoglobin-coated polystyrene latex bead films on pyrolytic graphite electrodes.

PubMed

Sun, Hong; Hu, Naifei

2004-08-01

A novel hemoglobin (Hb)-coated polystyrene (PS) latex bead film was deposited on pyrolytic graphite (PG) electrode surface. In the first step, positively charged Hb molecules in pH 5.0 buffers were adsorbed on the surface of negatively charged, 500 nm diameter PS latex beads bearing sulfate groups by electrostatic interaction. The aqueous dispersion of Hb-coated PS particles was then deposited on the surface of PG electrodes and, after evaporation of the solvent, Hb-PS films were formed. The Hb-PS film electrodes exhibited a pair of well-defined, quasi-reversible cyclic voltammetric (CV) peaks at about -0.36 V vs. SCE in pH 7.0 buffers, characteristic of Hb heme Fe(III)/Fe(II) redox couples. Positions of Soret absorption band of Hb-PS films suggest that Hb retains its near-native structure in the films in its dry form and in solution at medium pH. The Hb in PS films was also acted as a catalyst to catalyze electrochemical reduction of various substrates such as trichloroacetic acid (TCA), nitrite, oxygen and hydrogen peroxide.

Hydroxynaphthoquinone ultrathin films obtained by diazonium electroreduction: toward design of biosensitive electroactive interfaces.

PubMed

March, Gregory; Reisberg, Steeve; Piro, Benoit; Pham, Minh-Chau; Fave, Claire; Noel, Vincent

2010-05-01

Electroactive 2-(phenylsulfanyl)-8-hydroxy-1,4-naphthoquinone has been electrodeposited via the reduction of the corresponding diazonium salt on Au electrodes. Surface characterizations by X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IRRAS) reveal that the mechanism of film deposition follows an aryl radical formation and its immobilization on the electrode surface. Electrochemical study shows that the surface coverage can be finely tuned (thickness between one and four layers) by adjusting the potential and the deposition time. By managing the potential applied when reducing diazonium in potentiostatic mode, the formed layer could mediate or not charge transfer. This is the first time that the films obtained by diazonium process are demonstrated to act as mediators in the growth process. Hence, with potentials higher than the formal potential of quinone group, very thin and homogeneous layers are obtained, whereas thicker films are formed when more cathodic potentials than that of quinone are applied. The possibility to manage the charge-transfer kinetics, the thickness, and the homogeneity of electroactive deposits is interesting in the scope of designing electrochemical transducers.

Fabrication of nano copper oxide evenly patched on cubic sodium tantalate for oriented photocatalytic reduction of carbon dioxide.

PubMed

Xiang, Tianyu; Xin, Feng; Zhao, Can; Lou, Shuo; Qu, Wenxiu; Wang, Yong; Song, Yuexiao; Zhang, Shuangfang; Yin, Xiaohong

2018-05-15

A synthetic process was exploited to fabricate patchy CuO evenly planted on cubic NaTaO 3 for photocatalytically reducing CO 2 in isopropanol. The nano patches of CuO with about 15 nm in size were uniformly distributed on the surface of NaTaO 3 via a phase-transfer protocol and solvothermal synthesis. The crystal phase, morphology, composition, optical absorption and charge separation of as-prepared CuO-NaTaO 3 were characterized by XRD, SEM, TEM, EDX, XPS, UV-Vis and PL. The results of photocatalytic reduction of CO 2 confirmed that the CuO patched NaTaO 3 possessed better ability to separate charge carriers and selectively reduce CO 2 to methanol than CuO directly loaded NaTaO 3 using the traditional liquid phase reduction procedure after comparing the methanol yields. Furthermore, 5 wt% CuO patched NaTaO 3 led to the highest methanol yield of 1302.22 μmol g -1 h -1 . A redox mechanism was proposed and illustrated in a schematic diagram. Copyright © 2018 Elsevier Inc. All rights reserved.

Enhanced Visible-Light Photocatalytic H2 Evolution in Cu2O/Cu2Se Multilayer Heterostructure Nanowires Having {111} Facets and Physical Mechanism.

PubMed

Liu, Bin; Ning, Lichao; Zhang, Congjie; Zheng, Hairong; Liu, Shengzhong Frank; Yang, Heqing

2018-06-21

It is rather challenging to develop photocatalysts based on narrow-band-gap semiconductors for water splitting under solar irradiation. Herein, we synthesized the Cu 2 O/Cu 2 Se multilayer heterostructure nanowires exposing {111} crystal facets by a hydrothermal reaction of Se with Cu and KBH 4 in ethanol amine aqueous solution and subsequent annealing in air. The photocatalytic H 2 production activity of Cu 2 O/Cu 2 Se multilayer heterostructure nanowires is dramatically improved, with an increase on the texture coefficient of Cu 2 O(111) and Cu 2 Se(111) planes, and thus the exposed {111} facets may be the active surfaces for photocatalytic H 2 production. On the basis of the polar structure of Cu 2 O {111} and Cu 2 Se {111} surfaces, we presented a model of charge separation between the Cu-Cu 2 Se(111) and O-Cu 2 O(1̅ 1̅ 1̅) polar surfaces. An internal electric field is created between Cu-Cu 2 Se(111) and O-Cu 2 O(1̅ 1̅ 1̅) polar surfaces, because of spontaneous polarization. As a result, this internal electric field drives the photocreated charge separation. The oxidation and reduction reactions selectively occur at the negative O-Cu 2 O(1̅ 1̅ 1̅) and the positive Cu-Cu 2 Se(111) surfaces. The polar surface-engineering may be a general strategy for enhancing the photocatalytic H 2 -production activity of semiconductor photocatalysts. The charge separation mechanism not only can deepen the understanding of photocatalytic H 2 production mechanism but also provides a novel insight into the design of advanced photocatalysts, other photoelectric devices, and solar cells.

Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers.

PubMed

Leng, Chuan; Huang, Hao; Zhang, Kexin; Hung, Hsiang-Chieh; Xu, Yao; Li, Yaoxin; Jiang, Shaoyi; Chen, Zhan

2018-05-07

Interfacial water structure on a polymer surface in water (or surface hydration) is related to the antifouling activity of the polymer. Zwitterionic polymer materials exhibit excellent antifouling activity due to their strong surface hydration. It was proposed to replace zwitterionic polymers using mixed charged polymers because it is much easier to prepare mixed charged polymer samples with much lower costs. In this study, using sum frequency generation (SFG) vibrational spectroscopy, we investigated interfacial water structures on mixed charged polymer surfaces in water, and how such structures change while exposing to salt solutions and protein solutions. The 1:1 mixed charged polymer exhibits excellent antifouling property while other mixed charged polymers with different ratios of the positive/negative charges do not. It was found that on the 1:1 mixed charged polymer surface, SFG water signal is dominated by the contribution of the strongly hydrogen bonded water molecules, indicating strong hydration of the polymer surface. The responses of the 1:1 mixed charged polymer surface to salt solutions are similar to those of zwitterionic polymers. Interestingly, exposure to high concentrations of salt solutions leads to stronger hydration of the 1:1 mixed charged polymer surface after replacing the salt solution with water. Protein molecules do not substantially perturb the interfacial water structure on the 1:1 mixed charged polymer surface and do not adsorb to the surface, showing that this mixed charged polymer is an excellent antifouling material.

Charge Mediated Compaction and Rearrangement of Gas-Phase Proteins: A Case Study Considering Two Proteins at Opposing Ends of the Structure-Disorder Continuum

NASA Astrophysics Data System (ADS)

Jhingree, Jacquelyn R.; Bellina, Bruno; Pacholarz, Kamila J.; Barran, Perdita E.

2017-07-01

Charge reduction in the gas phase provides a direct means of manipulating protein charge state, and when coupled to ion mobility mass spectrometry (IM-MS), it is possible to monitor the effect of charge on protein conformation in the absence of solution. Use of the electron transfer reagent 1,3-dicyanobenzene, coupled with IM-MS, allows us to monitor the effect of charge reduction on the conformation of two proteins deliberately chosen from opposite sides of the order to disorder continuum: bovine pancreatic trypsin inhibitor (BPTI) and beta casein. The ordered BPTI presents compact conformers for each of three charge states accompanied by narrow collision cross-section distributions (TWCCSDN2→He). Upon reduction of BPTI, irrespective of precursor charge state, the TWCCSN2→He decreases to a similar distribution as found for the nESI generated ion of identical charge. The behavior of beta casein upon charge reduction is more complex. It presents over a wide charge state range (9-28), and intermediate charge states (13-18) have broad TWCCSDN2→He with multiple conformations, where both compaction and rearrangement are seen. Further, we see that the TWCCSDN2→He of the latter charge states are even affected by the presence of radical anions. Overall, we conclude that the flexible nature of some proteins result in broad conformational distributions comprised of many families, even for single charge states, and the barrier between different states can be easily overcome by an alteration of the net charge.

Effects of Discrete Charge Clustering in Simulations of Charged Interfaces.

PubMed

Grime, John M A; Khan, Malek O

2010-10-12

A system of counterions between charged surfaces is investigated, with the surfaces represented by uniform charged planes and three different arrangements of discrete surface charges - an equispaced grid and two different clustered arrangements. The behaviors of a series of systems with identical net surface charge density are examined, with particular emphasis placed on the long ranged corrections via the method of "charged slabs" and the effects of the simulation cell size. Marked differences are observed in counterion distributions and the osmotic pressure dependent on the particular representation of the charged surfaces; the uniformly charged surfaces and equispaced grids of discrete charge behave in a broadly similar manner, but the clustered systems display a pronounced decrease in osmotic pressure as the simulation size is increased. The influence of the long ranged correction is shown to be minimal for all but the very smallest of system sizes.

Charge transfer interactions in oligomer coated gold nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newmai, M. Boazbou; Kumar, Pandian Senthil, E-mail: duplasmonics@gmail.com

Gold nanoclusters were synthesized by a bottom-up synergistic approach of in-situ oligomerization of the monomer, N-vinyl pyrrolidone (NVP) and simultaneous weak reduction of Au-NVP complexes in the absence of any other external energy sources, thereby making these tiny gold clusters as the most elemental building blocks to construct further novel nano/microstructures with application potentials. It is well-known that metal clusters with less than 2 nm size do not show the usual surface plasmon band, because of the presence of a band-gap at the fermi level. Nevertheless, our present oligomer coated gold clusters show a discrete intense band at around 630 nm, whichmore » could very well be attributed to the charge transfer between the oligomer chain and the surface Au atoms. Such kind of sacrificial plasmon induced charge transfer interaction, observed for the very first time to the best of our knowledge, were also strongly corroborated through the enhancement / shifting of specific vibrational / rotational peaks as observed from the FTIR and Raman measurements as a function of the metal oxidation states, thus representing a new prototype for an efficient solar energy conversion probe.« less

A facile strategy to fabricate plasmonic Cu modified TiO{sub 2} nano-flower films for photocatalytic reduction of CO{sub 2} to methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Enzhou; Qi, Lulu; Bian, Juanjuan

Graphical abstract: Photoreduction of CO{sub 2} to CH{sub 3}OH over plasmonic Cu/TiO{sub 2} film. - Highlights: • Cu nanoparticles modified TiO{sub 2} nano-flower film was prepared by a facile strategy. • Cu nanoparticles can enhance the light absorption and the Raman scattering of TiO{sub 2}. • Cu nanoparticles can effectively restrain the recombination of the charge carriers. • A synergistic mechanism is proposed for photocatalytic reduction of CO{sub 2} on Cu/TiO{sub 2} film. - Abstract: Cu nanoparticles (NPs) deposited TiO{sub 2} nano-flower films were fabricated using a combination of a hydrothermal method and a microwave-assisted reduction process. The investigations indicatedmore » that Cu NPs and TiO{sub 2} film both exhibit visible light harvesting properties based on localized surface plasmon resonance (LSPR) of Cu NPs and unique nanostructures of TiO{sub 2} film. Fluorescence quenching was observed because the recombination of charge carriers was effectively suppressed by Cu NPs deposition. The experimental results indicate that Cu/TiO{sub 2} films exhibit better activity for the photocatalytic reduction of CO{sub 2} due to the charge transfer property and LSPR effect of Cu NPs. The CH{sub 3}OH production rate reached 1.8 μmol cm{sup −2} h{sup −1} (energy efficiency was 0.8%) over 0.5 Cu/TiO{sub 2} film under UV and visible light irradiation, which was 6.0 times higher than that observed over pure TiO{sub 2} film. In addition, a tentative photocatalytic mechanism is proposed to understand the experimental results over the Cu modified TiO{sub 2} nano-flower films.« less

Mechanism of H adatoms improving the O2 reduction reaction on the Zn-modified anatase TiO2 (101) surface studied by first principles calculation.

PubMed

Liu, Liangliang; Li, Chongyang; Jiang, Man; Li, Xiaodong; Huang, Xiaowei; Wang, Zhu; Jia, Yu

2018-06-05

First principles calculations were performed to cast insight into the mechanism of the improvement of O2 reduction reaction (ORR) activity by Zn and H interstitials on the anatase TiO2 (101) surface. For the Zn-modified anatase TiO2 (101) surface, both surface and subsurface Zn interstitials could contribute to O2 adsorption and dissociation, but the dissociation barriers of O2 molecules are still too high, which limits the ORR activity. After a H adatom is introduced onto the Zn-modified anatase TiO2 (101) surface, the highest energy barriers are greatly reduced compared with those of the Zn-modified surface. Meanwhile, it is observed that the dissociation barriers decrease almost linearly with the increase of the charge difference of adsorption O2 between initial and transition state configurations. Specifically, subsurface Zn and surface H interstitials facilitate O2 dissociation and subsequent oxidation reactions, and further frequency analysis shows that these dissociation processes are frequent even at the room temperature of 300 K. In a word, this work provides a theoretical support to design a high ORR activity catalyst of the TiO2 nanocrystal comparable to precious Pt catalysts.

Surface Reactivity of Li2MnO3: First-Principles and Experimental Study.

PubMed

Quesne-Turin, Ambroise; Flahaut, Delphine; Croguennec, Laurence; Vallverdu, Germain; Allouche, Joachim; Charles-Blin, Youn; Chotard, Jean-Noël; Ménétrier, Michel; Baraille, Isabelle

2017-12-20

This article deals with the surface reactivity of (001)-oriented Li 2 MnO 3 crystals investigated from a multitechnique approach combining material synthesis, X-ray photoemission spectroscopy (XPS), scanning electron microscopy, Auger electron spectroscopy, and first-principles calculations. Li 2 MnO 3 is considered as a model compound suitable to go further in the understanding of the role of tetravalent manganese atoms in the surface reactivity of layered lithium oxides. The knowledge of the surface properties of such materials is essential to understand the mechanisms involved in parasitic phenomena responsible for early aging or poor storage performances of lithium-ion batteries. The surface reactivity was probed through the adsorption of SO 2 gas molecules on large Li 2 MnO 3 crystals to be able to focus the XPS beam on the top of the (001) surface. A chemical mapping and XPS characterization of the material before and after SO 2 adsorption show in particular that the adsorption is homogeneous at the micro- and nanoscale and involves Mn reduction, whereas first-principles calculations on a slab model of the surface allow us to conclude that the most energetically favorable species formed is a sulfate with charge transfer implying reduction of Mn.

Studies of Surface Charging of Polymers by Indirect Triboelectrification

NASA Astrophysics Data System (ADS)

Mantovani, James; Calle, Carlos; Groop, Ellen; Buehler, Martin

2001-03-01

Charge is known to develop on the surface of an insulating polymer by frictional charging through direct physical contact with another material. We will present results of recent triboelectrification studies of polymer surfaces that utilized an indirect method of frictional charging. This method first involves placing a grounded thin metal foil in stationary contact over the polymer surface. The exposed metal foil is then rubbed with the surface of the material that generates the triboelectric charge. Data is presented for five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). The amount of charge that develops on an insulator's surface is measured using the MECA Electrometer, which was developed jointly by NASA Kennedy Space Center and the Jet Propulsion Laboratory to study the electrostatic properties of soil on the surface of Mars. Even though the insulator's surface is electrically shielded from the rubbing material by the grounded metal foil, charge measurements obtained by the MECA Electrometer after the metal foil is separated from the insulator's surface reveal that the insulator's surface does accumulate charge by indirect frictional charging. A possible explanation of the observations will be presented based on a simple contact barrier model.

Current-voltage characteristics influenced by the nanochannel diameter and surface charge density in a fluidic field-effect-transistor.

PubMed

Singh, Kunwar Pal; Guo, Chunlei

2017-06-21

The nanochannel diameter and surface charge density have a significant impact on current-voltage characteristics in a nanofluidic transistor. We have simulated the effect of the channel diameter and surface charge density on current-voltage characteristics of a fluidic nanochannel with positive surface charge on its walls and a gate electrode on its surface. Anion depletion/enrichment leads to a decrease/increase in ion current with gate potential. The ion current tends to increase linearly with gate potential for narrow channels at high surface charge densities and narrow channels are more effective to control the ion current at high surface charge densities. The current-voltage characteristics are highly nonlinear for wide channels at low surface charge densities and they show different regions of current change with gate potential. The ion current decreases with gate potential after attaining a peak value for wide channels at low values of surface charge densities. At low surface charge densities, the ion current can be controlled by a narrow range of gate potentials for wide channels. The current change with source drain voltage shows ohmic, limiting and overlimiting regions.

Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

NASA Astrophysics Data System (ADS)

Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

2015-10-01

Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems. Electronic supplementary information (ESI) available: Experimental procedures, synthesis, and characterization of molecules 1, 2 and 3. Explanation of the electrochemical method for approximating nanopore diameter. Additional XPS spectra. See DOI: 10.1039/C5NR02939B

5 CFR 1303.70 - Waiver or reduction of charges.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 5 Administrative Personnel 3 2011-01-01 2011-01-01 false Waiver or reduction of charges. 1303.70 Section 1303.70 Administrative Personnel OFFICE OF MANAGEMENT AND BUDGET ADMINISTRATIVE PROCEDURES PUBLIC INFORMATION PROVISIONS OF THE ADMINISTRATIVE PROCEDURES ACT Charges for Search and Reproduction § 1303.70...

5 CFR 1303.70 - Waiver or reduction of charges.

Code of Federal Regulations, 2010 CFR

2010-01-01

... 5 Administrative Personnel 3 2010-01-01 2010-01-01 false Waiver or reduction of charges. 1303.70 Section 1303.70 Administrative Personnel OFFICE OF MANAGEMENT AND BUDGET ADMINISTRATIVE PROCEDURES PUBLIC INFORMATION PROVISIONS OF THE ADMINISTRATIVE PROCEDURES ACT Charges for Search and Reproduction § 1303.70...

Effective Electrostatic Interactions Between Two Overall Neutral Surfaces with Quenched Charge Heterogeneity Over Atomic Length Scale

NASA Astrophysics Data System (ADS)

Zhou, S.

2017-12-01

Using Monte Carlo results as a reference, a classical density functional theory ( CDFT) is shown to reliably predict the forces between two heterogeneously charged surfaces immersed in an electrolyte solution, whereas the Poisson-Boltzmann ( PB) theory is demonstrated to deteriorate obviously for the same system even if the system parameters considered fall within the validity range of the PB theory in the homogeneously charged surfaces. By applying the tested CDFT, we study the effective electrostatic potential of mean force ( EPMF) between two face-face planar and hard surfaces of zero net charge on which positive and negative charges are separated and considered to present as discontinuous spots on the inside edges of the two surfaces. Main conclusions are summarized as follows: (i) strength of the EPMF in the surface charge separation case is very sensitively and positively correlated with the surface charge separation level and valency of the salt ion. Particularly, the charge separation level and the salt ion valency have a synergistic effect, which makes high limit of the EPMF strength in the surface charge separation case significantly go beyond that of the ideal homogeneously charged surface counterpart at average surface charge density similar to the average surface positive or negative charge density in the charge separation case. (ii) The surface charge distribution patterns mainly influence sign of the EPMF: symmetrical and asymmetrical patterns induce repulsive and attractive (at small distances) EPMF, respectively; but with low valency salt ions and low charge separation level the opposite may be the case. With simultaneous presence of both higher valency cation and anion, the EPMF can be repulsive at intermediate distances for asymmetrical patterns. (iii) Salt ion size has a significant impact, which makes the EPMF tend to become more and more repulsive with the ion diameter regardless of the surface charge distribution patterns and the valency of the salt ion; whereas if the 1:1 type electrolyte and the symmetrical patterns are considered, then the opposite may be the case. All of these findings can be explained self-consistently from several perspectives: an excess adsorption of the salt ions (induced by the surface charge separation) serving to raise the osmotic pressure between the plates, configuration fine-tuning in the thinner ion adsorption layer driven by the energy decrease principle, direct Coulombic interactions operating between charged objects on the two face-to-face plates involved, and net charge strength in the ion adsorption layer responsible for the net electrostatic repulsion.

Compilation of Blast Parameters of Selected High Explosives, Propellants, and Pyrotechnics in Surface Burst Configurations.

DTIC Science & Technology

1987-01-01

APPENDIX B- DATA REDUCTION PROGRAM .............................. 403 LIST OF ILLUSTRATIONS FIGURE NO. PAGE 1. Instrumented Test Pad Layout...weight to produce the same yield relative to hemis- pherical TNT. The test specimens were placed at ground zero in a particular in- plant geometry...The containers were either scaled from the original size or tested in full- scale configurations. The test charges were placed at ground zero and

Automated in-chamber specimen coating for serial block-face electron microscopy.

PubMed

Titze, B; Denk, W

2013-05-01

When imaging insulating specimens in a scanning electron microscope, negative charge accumulates locally ('sample charging'). The resulting electric fields distort signal amplitude, focus and image geometry, which can be avoided by coating the specimen with a conductive film prior to introducing it into the microscope chamber. This, however, is incompatible with serial block-face electron microscopy (SBEM), where imaging and surface removal cycles (by diamond knife or focused ion beam) alternate, with the sample remaining in place. Here we show that coating the sample after each cutting cycle with a 1-2 nm metallic film, using an electron beam evaporator that is integrated into the microscope chamber, eliminates charging effects for both backscattered (BSE) and secondary electron (SE) imaging. The reduction in signal-to-noise ratio (SNR) caused by the film is smaller than that caused by the widely used low-vacuum method. Sample surfaces as large as 12 mm across were coated and imaged without charging effects at beam currents as high as 25 nA. The coatings also enabled the use of beam deceleration for non-conducting samples, leading to substantial SNR gains for BSE contrast. We modified and automated the evaporator to enable the acquisition of SBEM stacks, and demonstrated the acquisition of stacks of over 1000 successive cut/coat/image cycles and of stacks using beam deceleration or SE contrast. © 2013 The Authors Journal of Microscopy © 2013 Royal Microscopical Society.

Battery Charge Affects the Stability of Light Intensity from Light-emitting Diode Light-curing Units.

PubMed

Tongtaksin, A; Leevailoj, C

This study investigated the influence of battery charge levels on the stability of light-emitting diode (LED) curing-light intensity by measuring the intensity from fully charged through fully discharged batteries. The microhardness of resin composites polymerized by the light-curing units at various battery charge levels was measured. The light intensities of seven fully charged battery LED light-curing units-1) LY-A180, 2) Bluephase, 3) Woodpecker, 4) Demi Plus, 5) Saab II, 6) Elipar S10, and 7) MiniLED-were measured with a radiometer (Kerr) after every 10 uses (20 seconds per use) until the battery was discharged. Ten 2-mm-thick cylindrical specimens of A3 shade nanofilled resin composite (PREMISE, Kerr) were prepared per LED light-curing unit group. Each specimen was irradiated by the fully charged light-curing unit for 20 seconds. The LED light-curing units were then used until the battery charge fell to 50%. Specimens were prepared again as described above. This was repeated again when the light-curing units' battery charge fell to 25% and when the light intensity had decreased to 400 mW/cm 2 . The top/bottom surface Knoop hardness ratios of the specimens were determined. The microhardness data were analyzed by one-way analysis of variance with Tukey test at a significance level of 0.05. The Pearson correlation coefficient was used to determine significant correlations between surface hardness and light intensity. We found that the light intensities of the Bluephase, Demi Plus, and Elipar S10 units were stable. The intensity of the MiniLED unit decreased slightly; however, it remained above 400 mW/cm 2 . In contrast, the intensities of the LY-A180, Woodpecker, and Saab II units decreased below 400 mW/cm 2 . There was also a significant decrease in the surface microhardnesses of the resin composite specimens treated with MiniLED, LY-A180, Woodpecker, and Saab II. In conclusion, the light intensity of several LED light-curing units decreased as the battery was discharged, with a coincident reduction in the units' ability to polymerize resin composite. Therefore, the intensity of an LED light-curing unit should be evaluated during the life of its battery charge to ensure that sufficient light intensity is being generated.

Rectification of nanopores at surfaces

PubMed Central

Sa, Niya

2011-01-01

At the nanoscale, methods to measure surface charge can prove challenging. Herein we describe a general method to report surface charge through the measurement of ion current rectification of a nanopipette brought in close proximity to a charged substrate. This method is able to discriminate between charged cationic and anionic substrates when the nanopipette is brought within distances from ten to hundreds of nanometers from the surface. Further studies of the pH dependence on the observed rectification support a surface-induced mechanism and demonstrate the ability to further discriminate between cationic and nominally uncharged surfaces. This method could find application in measurement and mapping of heterogeneous surface charges and is particularly attractive for future biological measurements, where noninvasive, noncontact probing of surface charge will prove valuable. PMID:21675734

The electrokinetic behavior of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1988-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chrondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for chemical adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopopolysacchrides have greater affinity for the COM surface than the proteins. The amount of proteins that can chemically adsorb appears to be limited to approximately one monomolecular layer. When the surface charge is high, an insufficient number of proteins can chemically adsorb to neutralize or reverse the surface charge. The remaining surface charge is balanced by proteins held near the surface by longer range electrostatic forces only. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

Protein adsorption at charged surfaces: the role of electrostatic interactions and interfacial charge regulation.

PubMed

Hartvig, Rune A; van de Weert, Marco; Østergaard, Jesper; Jorgensen, Lene; Jensen, Henrik

2011-03-15

The understanding of protein adsorption at charged surfaces is important for a wide range of scientific disciplines including surface engineering, separation sciences and pharmaceutical sciences. Compared to chemical entities having a permanent charge, the adsorption of small ampholytes and proteins is more complicated as the pH near a charged surface can be significantly different from the value in bulk solution. In this work, we have developed a phenomenological adsorption model which takes into account the combined role of interfacial ion distribution, interfacial charge regulation of amino acids in the proximity of the surface, electroneutrality, and mass balance. The model is straightforward to apply to a given set of experimental conditions as most model parameters are obtained from bulk properties and therefore easy to estimate or are directly measurable. The model provides a detailed understanding of the importance of surface charge on adsorption and in particular of how changes in surface charge, concentration, and surface area may affect adsorption behavior. The model is successfully used to explain the experimental adsorption behavior of the two model proteins lysozyme and α-lactalbumin. It is demonstrated that it is possible to predict the pH and surface charge dependent adsorption behavior from experimental or theoretical estimates of a preferred orientation of a protein at a solid charged interface.

The Charging Events in Contact-Separation Electrification.

PubMed

Musa, Umar G; Cezan, S Doruk; Baytekin, Bilge; Baytekin, H Tarik

2018-02-06

Contact electrification (CE)-charging of surfaces that are contacted and separated, is a common phenomenon, however it is not completely understood yet. Recent studies using surface imaging techniques and chemical analysis revealed a 'spatial' bipolar distribution of charges at the nano dimension, which made a paradigm shift in the field. However, such analyses can only provide information about the charges that remained on the surface after the separation, providing limited information about the actual course of the CE event. Tapping common polymers and metal surfaces to each other and detecting the electrical potential produced on these surfaces 'in-situ' in individual events of contact and separation, we show that, charges are generated and transferred between the surfaces in both events; the measured potential is bipolar in contact and unipolar in separation. We show, the 'contact-charges' on the surfaces are indeed the net charges that results after the separation process, and a large contribution to tribocharge harvesting comes, in fact, from the electrostatic induction resulting from the generated CE charges. Our results refine the mechanism of CE providing information for rethinking the conventional ranking of materials' charging abilities, charge harvesting, and charge prevention.

Charged particle detectors with active detector surface for partial energy deposition of the charged particles and related methods

DOEpatents

Gerts, David W; Bean, Robert S; Metcalf, Richard R

2013-02-19

A radiation detector is disclosed. The radiation detector comprises an active detector surface configured to generate charge carriers in response to charged particles associated with incident radiation. The active detector surface is further configured with a sufficient thickness for a partial energy deposition of the charged particles to occur and permit the charged particles to pass through the active detector surface. The radiation detector further comprises a plurality of voltage leads coupled to the active detector surface. The plurality of voltage leads is configured to couple to a voltage source to generate a voltage drop across the active detector surface and to separate the charge carriers into a plurality of electrons and holes for detection. The active detector surface may comprise one or more graphene layers. Timing data between active detector surfaces may be used to determine energy of the incident radiation. Other apparatuses and methods are disclosed herein.

Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

PubMed

Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

2005-03-17

Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH < or = 5, on polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

NASA charging analyzer program: A computer tool that can evaluate electrostatic contamination

NASA Technical Reports Server (NTRS)

Stevens, N. J.; Roche, J. C.; Mandell, M. J.

1978-01-01

A computer code, the NASA Charging Analyzer Program (NASCAP), was developed to study the surface charging of bodies subjected to geomagnetic substorm conditions. This program will treat the material properties of a surface in a self-consistent manner and calculate the electric fields in space due to the surface charge. Trajectories of charged particles in this electric field can be computed to determine if these particles enhance surface contamination. A preliminary model of the Spacecraft Charging At The High Altitudes (SCATHA) satellite was developed in the NASCAP code and subjected to a geomagnetic substorm environment to investigate the possibility of electrostatic contamination. The results indicate that differential voltages will exist between the spacecraft ground surfaces and the insulator surfaces. The electric fields from this differential charging can enhance the contamination of spacecraft surfaces.

Adhesion of osteoblasts to a nanorough titanium implant surface

PubMed Central

Gongadze, Ekaterina; Kabaso, Doron; Bauer, Sebastian; Slivnik, Tomaž; Schmuki, Patrik; van Rienen, Ursula; Iglič, Aleš

2011-01-01

This work considers the adhesion of cells to a nanorough titanium implant surface with sharp edges. The basic assumption was that the attraction between the negatively charged titanium surface and a negatively charged osteoblast is mediated by charged proteins with a distinctive quadrupolar internal charge distribution. Similarly, cation-mediated attraction between fibronectin molecules and the titanium surface is expected to be more efficient for a high surface charge density, resulting in facilitated integrin mediated osteoblast adhesion. We suggest that osteoblasts are most strongly bound along the sharp convex edges or spikes of nanorough titanium surfaces where the magnitude of the negative surface charge density is the highest. It is therefore plausible that nanorough regions of titanium surfaces with sharp edges and spikes promote the adhesion of osteoblasts. PMID:21931478

Open carbon nanopipettes as resistive-pulse sensors, rectification sensors, and electrochemical nanoprobes.

PubMed

Hu, Keke; Wang, Yixian; Cai, Huijing; Mirkin, Michael V; Gao, Yang; Friedman, Gary; Gogotsi, Yury

2014-09-16

Nanometer-sized glass and quartz pipettes have been widely used as a core of chemical sensors, patch clamps, and scanning probe microscope tips. Many of those applications require the control of the surface charge and chemical state of the inner pipette wall. Both objectives can be attained by coating the inner wall of a quartz pipette with a nanometer-thick layer of carbon. In this letter, we demonstrate the possibility of using open carbon nanopipettes (CNP) produced by chemical vapor deposition as resistive-pulse sensors, rectification sensors, and electrochemical nanoprobes. By applying a potential to the carbon layer, one can change the surface charge and electrical double-layer at the pipette wall, which, in turn, affect the ion current rectification and adsorption/desorption processes essential for resistive-pulse sensors. CNPs can also be used as versatile electrochemical probes such as asymmetric bipolar nanoelectrodes and dual electrodes based on simultaneous recording of the ion current through the pipette and the current produced by oxidation/reduction of molecules at the carbon nanoring.

Thermal treatment effects on charge storage performance of graphene-based materials for supercapacitors.

PubMed

Zhang, Hongxin; Bhat, Vinay V; Gallego, Nidia C; Contescu, Cristian I

2012-06-27

Graphene materials were synthesized by reduction of exfoliated graphite oxide and then thermally treated in nitrogen to improve the surface area and their electrochemical performance as electrical double-layer capacitor electrodes. The structural and surface properties of the prepared reduced graphite oxide (RGO) were investigated using atomic force microscopy, scanning electron microscopy, Raman spectra, X-ray diffraction pattern analysis, and nitrogen adsorption/desorption studies. RGO forms a continuous network of crumpled sheets, which consist of large amounts of few-layer and single-layer graphenes. Electrochemical studies were conducted by cyclic voltammetry, impedance spectroscopy, and galvanostatic charge-discharge measurements. The modified RGO materials showed enhanced electrochemical performance, with maximum specific capacitance of 96 F/g, energy density of 12.8 Wh/kg, and power density of 160 kW/kg. These results demonstrate that thermal treatment of RGO at selected conditions is a convenient and efficient method for improving its specific capacitance, energy, and power density.

Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers.

PubMed

Gan, Zecheng; Xing, Xiangjun; Xu, Zhenli

2012-07-21

We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layer structures in electrolyte solutions with divalent counterions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: (1) SURF1 with uniform surface charges, (2) SURF2 with discrete point charges on the interface, and (3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function and the zeta potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes, have significant impacts on zeta potentials of electric double layers.

Hydrophobicity and Charge Shape Cellular Metabolite Concentrations

PubMed Central

Bar-Even, Arren; Noor, Elad; Flamholz, Avi; Buescher, Joerg M.; Milo, Ron

2011-01-01

What governs the concentrations of metabolites within living cells? Beyond specific metabolic and enzymatic considerations, are there global trends that affect their values? We hypothesize that the physico-chemical properties of metabolites considerably affect their in-vivo concentrations. The recently achieved experimental capability to measure the concentrations of many metabolites simultaneously has made the testing of this hypothesis possible. Here, we analyze such recently available data sets of metabolite concentrations within E. coli, S. cerevisiae, B. subtilis and human. Overall, these data sets encompass more than twenty conditions, each containing dozens (28-108) of simultaneously measured metabolites. We test for correlations with various physico-chemical properties and find that the number of charged atoms, non-polar surface area, lipophilicity and solubility consistently correlate with concentration. In most data sets, a change in one of these properties elicits a ∼100 fold increase in metabolite concentrations. We find that the non-polar surface area and number of charged atoms account for almost half of the variation in concentrations in the most reliable and comprehensive data set. Analyzing specific groups of metabolites, such as amino-acids or phosphorylated nucleotides, reveals even a higher dependence of concentration on hydrophobicity. We suggest that these findings can be explained by evolutionary constraints imposed on metabolite concentrations and discuss possible selective pressures that can account for them. These include the reduction of solute leakage through the lipid membrane, avoidance of deleterious aggregates and reduction of non-specific hydrophobic binding. By highlighting the global constraints imposed on metabolic pathways, future research could shed light onto aspects of biochemical evolution and the chemical constraints that bound metabolic engineering efforts. PMID:21998563

Synthesis of Self-Assembled Multifunctional Nanocomposite Catalysts with Highly Stabilized Reactivity and Magnetic Recyclability

NASA Astrophysics Data System (ADS)

Yu, Xu; Cheng, Gong; Zheng, Si-Yang

2016-05-01

In this paper, a multifunctional Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite catalyst with highly stabilized reactivity and magnetic recyclability was synthesized by a self-assembled method. The magnetic Fe3O4 nanoparticles were coated with a thin layer of the SiO2 to obtain a negatively charged surface. Then positively charged poly(ethyleneimine) polymer (PEI) was self-assembled onto the Fe3O4@SiO2 by electrostatic interaction. Next, negatively charged glutathione capped gold nanoparticles (GSH-AuNPs) were electrostatically self-assembled onto the Fe3O4@SiO2@PEI. After that, silver was grown on the surface of the nanocomposite due to the reduction of the dopamine in the alkaline solution. An about 5 nm thick layer of polydopamine (PDA) was observed to form the Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was carefully characterized by the SEM, TEM, FT-IR, XRD and so on. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite shows a high saturation magnetization (Ms) of 48.9 emu/g, which allows it to be attracted rapidly to a magnet. The Fe3O4@SiO2@PEI-Au/Ag@PDA nanocomposite was used to catalyze the reduction of p-nitrophenol (4-NP) to p-aminophenol (4-AP) as a model system. The reaction kinetic constant k was measured to be about 0.56 min-1 (R2 = 0.974). Furthermore, the as-prepared catalyst can be easily recovered and reused for 8 times, which didn’t show much decrease of the catalytic capability.

The role of iron-oxide aerosols and sunlight in the atmospheric reduction of Hg(II) species: A DFT+ U study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tacey, Sean A.; Szilvasi, Tibor; Xu, Lang

Experimental and field measurements have shown that, in the presence of both iron-containing aerosols and sunlight, oxidized mercury species such as HgCl 2 and HgBr 2 undergo reduction to elemental mercury (Hg°), which remains in the atmosphere longer than oxidized mercury species due to its higher volatility. We performed density functional theory (DFT, PW91+U) calculations to elucidate the reduction mechanism for atmospheric HgCl 2 and HgBr 2 to Hg° on several iron-oxide aerosol surfaces relevant in the troposphere. On the OH-Fe-R-terminated α-Fe 2O 3(0001) surface, predicted to be most prevalent under ambient conditions, we show that: (1) the first Hg-Xmore » bond is broken via either thermal or photolytic activation depending on the ambient temperature; (2) photons with an energy of 2.69 eV (461 nm) are required to break the second Hg-X bond; and (3) a photo-induced surface-to-adsorbate charge-transfer process can promote Hg° desorption with an excitation energy of 2.59 eV (479 nm). All the calculated excitation energies are below the threshold value of 3.9 eV (320 nm) for photons in the troposphere, suggesting that sunlight can facilitate mercury reduction on iron-oxide aerosol surfaces. In contrast, the gas-phase reduction of HgCl 2 (HgBr 2) involves photoexcitation requiring an energy of 4.98 (4.45) eV (249 (279) nm); therefore, the energy range of sunlight is not suitable for gas-phase reduction. Our computational results provide the first evidence on the detailed mechanism for the combined role of aerosols and photons in the reduction of HgCl 2 and HgBr 2. In conclusion, our methodology can be adapted to study other photochemical heterogeneous processes in the atmosphere.« less

The role of iron-oxide aerosols and sunlight in the atmospheric reduction of Hg(II) species: A DFT+ U study

DOE PAGES

Tacey, Sean A.; Szilvasi, Tibor; Xu, Lang; ...

2018-04-22

Experimental and field measurements have shown that, in the presence of both iron-containing aerosols and sunlight, oxidized mercury species such as HgCl 2 and HgBr 2 undergo reduction to elemental mercury (Hg°), which remains in the atmosphere longer than oxidized mercury species due to its higher volatility. We performed density functional theory (DFT, PW91+U) calculations to elucidate the reduction mechanism for atmospheric HgCl 2 and HgBr 2 to Hg° on several iron-oxide aerosol surfaces relevant in the troposphere. On the OH-Fe-R-terminated α-Fe 2O 3(0001) surface, predicted to be most prevalent under ambient conditions, we show that: (1) the first Hg-Xmore » bond is broken via either thermal or photolytic activation depending on the ambient temperature; (2) photons with an energy of 2.69 eV (461 nm) are required to break the second Hg-X bond; and (3) a photo-induced surface-to-adsorbate charge-transfer process can promote Hg° desorption with an excitation energy of 2.59 eV (479 nm). All the calculated excitation energies are below the threshold value of 3.9 eV (320 nm) for photons in the troposphere, suggesting that sunlight can facilitate mercury reduction on iron-oxide aerosol surfaces. In contrast, the gas-phase reduction of HgCl 2 (HgBr 2) involves photoexcitation requiring an energy of 4.98 (4.45) eV (249 (279) nm); therefore, the energy range of sunlight is not suitable for gas-phase reduction. Our computational results provide the first evidence on the detailed mechanism for the combined role of aerosols and photons in the reduction of HgCl 2 and HgBr 2. In conclusion, our methodology can be adapted to study other photochemical heterogeneous processes in the atmosphere.« less

Carbon-doped boron nitride nanosheet as a promising catalyst for N2O reduction by CO or SO2 molecule: A comparative DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Saeidi, Nasibeh

2018-06-01

We report for the first time, the catalytic activity of the experimentally available carbon-doped boron nitride nanosheet (C-BNNS) towards the reduction of N2O in the presence of CO or SO2 molecule. According to our density functional theory calculations, C-doping can introduce high spin density into BN monolayer which is mainly localized over the C and its neighboring N atoms. The Hirshfeld charge density analysis reveals that the electron-rich C-BNNS acts as an electron donating support to activate N2O molecule which is an important step in the reduction of N2O. The N2O reduction reaction starts with the dissociative adsorption of N2O over the C-BNNS surface, yielding the N2 molecule and an activated oxygen moiety (Oads) adsorbed over the C atom. The reaction then proceeds via the elimination of Oads by a CO or SO2 molecule. The obtained low activation energies clearly indicate that the metal-free C-BNNS surface can be regarded as a highly active catalyst for the reduction of N2O. The results of this study may open new avenues in searching low cost and highly active BN-based catalysts for low temperature reduction of N2O.

Nanopipette delivery: influence of surface charge.

PubMed

Shi, Wenqing; Sa, Niya; Thakar, Rahul; Baker, Lane A

2015-07-21

In this report, transport through a nanopipette is studied and the interplay between current rectification and ion delivery for small pipettes is examined. First, surface charge dependence of concentration polarization effects in a quartz nanopipette was investigated. Electrical characterization was performed through current-potential (I-V) measurements. In addition, fluorescein (an anionic fluorescent probe) was utilized to optically map ion enrichment and ion depletion in the nanopipette tip. Bare nanopipettes and polyethylenimine (PEI)-modified nanopipettes were examined. Results confirm that concentration polarization is a surface charge dependent phenomenon and delivery can be controlled through modification of surface charge. The relationship between concentration polarization effects and voltage-driven delivery of charged electroactive species was investigated with a carbon ring/nanopore electrode fabricated from pyrolyzed parylene C (PPC). Factors such as surface charge polarity of the nanopipette, electrolyte pH, and electrolyte concentration were investigated. Results indicate that with modification of surface charge, additional control over delivery of charged species can be achieved.

Enhanced catalyst activity by decorating of Au on Ag@Cu2O nanoshell

NASA Astrophysics Data System (ADS)

Chen, Lei; Liu, Maomao; Zhao, Yue; Kou, Qiangwei; Wang, Yaxin; Liu, Yang; Zhang, Yongjun; Yang, Jinghai; Jung, Young Mee

2018-03-01

We successfully synthesized Au-decorated Ag@Cu2O heterostructures via a simple galvanic replacement method. As the Au precursor concentration increased, the density of the Au nanoparticles (NPs) on the Ag@Cu2O surface increased, which changed the catalytic activity of the Ag@Cu2O-Au structure. The combination of Au, Ag, and Cu2O exhibited excellent catalytic properties, which can further effect on the catalyst activity of the Ag@Cu2O-Au structure. In addition, the proposed Ag@Cu2O-Au nanocomposite was used to transform the organic, toxic pollutant, 4-nitrophenol (4-NP), into its nontoxic and medicinally important amino derivative via a catalytic reduction to optimize the material performance. The proposed Au-decorated Ag@Cu2O exhibited excellent catalytic activity, and the catalytic reduction time greatly decreased (5 min). Thus, three novel properties of Ag@Cu2O-Au, i.e., charge redistribution and transfer, adsorption, and catalytic reduction of organic pollutants, were ascertained for water remediation. The proposed catalytic properties have potential applications for photocatalysis and localized surface plasmon resonance (LSPR)- and peroxidase-like catalysis.

Polarization-induced surface charges in hydroxyapatite ceramics

NASA Astrophysics Data System (ADS)

Horiuchi, N.; Nakaguki, S.; Wada, N.; Nozaki, K.; Nakamura, M.; Nagai, A.; Katayama, K.; Yamashita, K.

2014-07-01

Calcium hydroxyapatite (HAp; Ca10(PO4)6(OH)2) is a well-known biomaterial that is the main inorganic component of bones and teeth. Control over the surface charge on HAp would be a key advance in the development of the material for tissue engineering. We demonstrate here that surface charge can be induced by an electrical poling process using the Kelvin method. Positive and negative charges were induced on the HAp surface in response to the applied electric field in the poling process. The surface charging is attributed to dipole polarization that is homogeneously distributed in HAp. Additionally, the surface charging is considered to originate from the organization of OH- ions into a polar phase in the structure.

Sanitizer Efficacy against Murine Norovirus, a Surrogate for Human Norovirus, on Stainless Steel Surfaces when Using Three Application Methods

PubMed Central

Kotwal, Grishma; Harrison, Mark A.; Law, S. Edward; Harrison, Judy A.

2013-01-01

Human noroviruses are major etiologic agents of epidemic gastroenteritis. Outbreaks are often accompanied by contamination of environmental surfaces, but since these viruses cannot be routinely propagated in laboratory cultures, their response to surface disinfectants is predicted by using surrogates, such as murine norovirus 1 (MNV-1). This study compared the virucidal efficacies of various liquid treatments (three sanitizer liquids, 5% levulinic acid plus 2% SDS [LEV/SDS], 200 ppm chlorine, and an isopropanol-based quaternary ammonium compound [Alpet D2], and two control liquids, sterile tap water and sterile tap water plus 2% SDS) when delivered to MNV-1-inoculated stainless steel surfaces by conventional hydraulic or air-assisted, induction-charged (AAIC) electrostatic spraying or by wiping with impregnated towelettes. For the spray treatments, LEV/SDS proved effective when applied with hydraulic and AAIC electrostatic spraying, providing virus reductions of 2.71 and 1.66 log PFU/ml, respectively. Alpet D2 provided a 2.23-log PFU/ml reduction with hydraulic spraying, outperforming chlorine (1.16-log PFU/ml reduction). Chlorine and LEV/SDS were equally effective as wipes, reducing the viral load by 7.05 log PFU/ml. Controls reduced the viral load by <1 log with spraying applications and by >3 log PFU/ml with wiping. Results indicated that both sanitizer type and application methods should be carefully considered when choosing a surface disinfectant to best prevent and control environmental contamination by noroviruses. PMID:23263949

Poisson-Boltzmann theory of the charge-induced adsorption of semi-flexible polyelectrolytes.

PubMed

Ubbink, Job; Khokhlov, Alexei R

2004-03-15

A model is suggested for the structure of an adsorbed layer of a highly charged semi-flexible polyelectrolyte on a weakly charged surface of opposite charge sign. The adsorbed phase is thin, owing to the effective reversal of the charge sign of the surface upon adsorption, and ordered, owing to the high surface density of polyelectrolyte strands caused by the generally strong binding between polyelectrolyte and surface. The Poisson-Boltzmann equation for the electrostatic interaction between the array of adsorbed polyelectrolytes and the charged surface is solved for a cylindrical geometry, both numerically, using a finite element method, and analytically within the weak curvature limit under the assumption of excess monovalent salt. For small separations, repulsive surface polarization and counterion osmotic pressure effects dominate over the electrostatic attraction and the resulting electrostatic interaction curve shows a minimum at nonzero separations on the Angstrom scale. The equilibrium density of the adsorbed phase is obtained by minimizing the total free energy under the condition of equality of chemical potential and osmotic pressure of the polyelectrolyte in solution and in the adsorbed phase. For a wide range of ionic conditions and charge densities of the charged surface, the interstrand separation as predicted by the Poisson-Boltzmann model and the analytical theory closely agree. For low to moderate charge densities of the adsorbing surface, the interstrand spacing decreases as a function of the charge density of the charged surface. Above about 0.1 M excess monovalent salt, it is only weakly dependent on the ionic strength. At high charge densities of the adsorbing surface, the interstrand spacing increases with increasing ionic strength, in line with the experiments by Fang and Yang [J. Phys. Chem. B 101, 441 (1997)]. (c) 2004 American Institute of Physics.

Evaluation of reduced point charge models of proteins through Molecular Dynamics simulations: application to the Vps27 UIM-1-Ubiquitin complex.

PubMed

Leherte, Laurence; Vercauteren, Daniel P

2014-02-01

Reduced point charge models of amino acids are designed, (i) from local extrema positions in charge density distribution functions built from the Poisson equation applied to smoothed molecular electrostatic potential (MEP) functions, and (ii) from local maxima positions in promolecular electron density distribution functions. Corresponding charge values are fitted versus all-atom Amber99 MEPs. To easily generate reduced point charge models for protein structures, libraries of amino acid templates are built. The program GROMACS is used to generate stable Molecular Dynamics trajectories of an Ubiquitin-ligand complex (PDB: 1Q0W), under various implementation schemes, solvation, and temperature conditions. Point charges that are not located on atoms are considered as virtual sites with a nul mass and radius. The results illustrate how the intra- and inter-molecular H-bond interactions are affected by the degree of reduction of the point charge models and give directions for their implementation; a special attention to the atoms selected to locate the virtual sites and to the Coulomb-14 interactions is needed. Results obtained at various temperatures suggest that the use of reduced point charge models allows to probe local potential hyper-surface minima that are similar to the all-atom ones, but are characterized by lower energy barriers. It enables to generate various conformations of the protein complex more rapidly than the all-atom point charge representation. Copyright © 2013 Elsevier Inc. All rights reserved.

Soft Landing of Mass-Selected Gold Clusters: Influence of Ion and Ligand on Charge Retention and Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Laskin, Julia

Herein, we employ a combination of reduction synthesis in solution, soft landing of mass-selected precursor and product ions, and in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) to examine the influence of ion and the length of diphosphine ligands on the charge retention and reactivity of ligated gold clusters deposited onto self-assembled monolayer surfaces (SAMs). Product ions (Au10L42+, (10,4)2+, L = 1,3-bis(diphenyl-phosphino)propane, DPPP) were prepared through in-source collision induced dissociation (CID) and precursor ions [(8,4)2+, L = 1,6-bis(diphenylphosphino)hexane, DPPH] were synthesized in solution for comparison to (11,5)3+ precursor ions ligated with DPPP investigated previously (ACS Nano 2012, 6, 573 andmore » J. Phys. Chem. C. 2012, 116, 24977). Similar to (11,5)3+ precursor ions, the (10,4)2+ product ions are shown to retain charge on 1H,1H,2H,2H-perfluorodecanethiol monolayers (FSAMs). Additional abundant peaks at higher m/z indicative of reactivity are observed in the TOF-SIMS spectrum of (10,4)2+ product ions that are not seen for (11,5)3+ precursor ions. The abundance of (10,4)2+ on 16-mercaptohexadecanoic acid (COOH-SAMs) is demonstrated to be lower than on FSAMs, consistent with partial reduction of charge. The (10,4)2+ product ion on 1-dodecanethiol (HSAMs) exhibits peaks similar to those seen on the COOH-SAM. On the HSAM, higher m/z peaks indicative of reactivity are observed similar to those on the FSAM. The (8,4)2+ DPPH precursor ions are shown to retain charge on FSAMs similar to (11,5)3+ precursor ions prepared with DPPP. An additional peak corresponding to attachment of one gold atom to (8,4)2+ is observed at higher m/z for DPPH-ligated clusters. On the COOH-SAM, (8,4)2+ is less abundant than on the FSAM consistent with partial neutralization. The results indicate that although retention of charge by product ions generated by CID is similar to precursor ions their reactivity during analysis with SIMS is different resulting in the formation of peaks corresponding to reaction products. The length of the ligand exerts only a minor influence on the charge retention and reactivity of gold clusters. Based on the observed reactivity of (10,4)2+ it is anticipated that in-source CID will be increasingly applied for the preparation of a distribution of product ions, including undercoordinated and reactive species, for soft landing onto surfaces.« less

Method for Estimating the Charge Density Distribution on a Dielectric Surface.

PubMed

Nakashima, Takuya; Suhara, Hiroyuki; Murata, Hidekazu; Shimoyama, Hiroshi

2017-06-01

High-quality color output from digital photocopiers and laser printers is in strong demand, motivating attempts to achieve fine dot reproducibility and stability. The resolution of a digital photocopier depends on the charge density distribution on the organic photoconductor surface; however, directly measuring the charge density distribution is impossible. In this study, we propose a new electron optical instrument that can rapidly measure the electrostatic latent image on an organic photoconductor surface, which is a dielectric surface, as well as a novel method to quantitatively estimate the charge density distribution on a dielectric surface by combining experimental data obtained from the apparatus via a computer simulation. In the computer simulation, an improved three-dimensional boundary charge density method (BCM) is used for electric field analysis in the vicinity of the dielectric material with a charge density distribution. This method enables us to estimate the profile and quantity of the charge density distribution on a dielectric surface with a resolution of the order of microns. Furthermore, the surface potential on the dielectric surface can be immediately calculated using the obtained charge density. This method enables the relation between the charge pattern on the organic photoconductor surface and toner particle behavior to be studied; an understanding regarding the same may lead to the development of a new generation of higher resolution photocopiers.

Summary of SLAC's SEY Measurement On Flat Accelerator Wall Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Le Pimpec, F.; /PSI, Villigen /SLAC

The electron cloud effect (ECE) causes beam instabilities in accelerator structures with intense positively charged bunched beams. Reduction of the secondary electron yield (SEY) of the beam pipe inner wall is effective in controlling cloud formation. We summarize SEY results obtained from flat TiN, TiZrV and Al surfaces carried out in a laboratory environment. SEY was measured after thermal conditioning, as well as after low energy, less than 300 eV, particle exposure.

Affinity Electrophoresis Using Ligands Attached To Polymers

NASA Technical Reports Server (NTRS)

Van Alstine, James M.; Snyder, Robert S.; Harris, J. M.; Brooks, D. E.

1990-01-01

In new technique, reduction of electrophoretic mobilities by addition of polyethylene glycol to ligands increases electrophoretic separabilities. In immuno-affinity electrophoresis, modification of ligands extends specificity of electrophoretic separation to particles having surface electric-charge structures otherwise making them electrophoretically inseparable. Modification of antibodies by polyethylene glycol greatly reduces ability to aggregate while enhancing ability to affect electrophoretic mobilities of cells. In hydrophobic-affinity electrophoresis, addition of polyethylene glycol reduces tendency toward aggregation of cells or macromolecules.

Lunar Surface Charging during Solar Energetic Particle Events

NASA Astrophysics Data System (ADS)

Halekas, Jasper S.; Delory, G. T.; Mewaldt, R. A.; Lin, R. P.; Fillingim, M. O.; Brain, D. A.; Lee, C. O.; Stubbs, T. J.; Farrell, W. M.; Hudson, M. K.

2006-09-01

The surface of the Moon, not protected by any substantial atmosphere, is directly exposed to the impact of both solar UV and solar wind plasma and energetic particles. This creates a complex lunar electrostatic environment, with the surface typically charging slightly positive in sunlight, and negative in shadow. Observations from the Apollo era and theoretical considerations strongly suggest that surface charging leads to dust electrification and transport, posing a potentially significant hazard for exploration. The most significant charging effects should occur when the Moon is exposed to high-temperature plasmas like those encountered in the terrestrial plasmasheet or in solar storms. We now present evidence for kilovolt-scale negative charging of the shadowed lunar surface during solar energetic particle (SEP) events, utilizing data from the Lunar Prospector Electron Reflectometer (LP ER). We find that SEP events are associated with the most extreme lunar surface charging observed during the LP mission - rivaled only by previously reported charging during traversals of the terrestrial plasmasheet. The largest charging event observed by LP is a 4 kV negative surface potential (as compared to typical values of V) during a SEP event in May 1998. We characterize lunar surface charging during several SEP events, and compare to energetic particle measurements from ACE, Wind, and SOHO in order to determine the relationship between SEP events and extreme lunar surface charging. Space weather events are already considered by NASA to be a significant hazard to lunar exploration, due to high-energy ionizing radiation. Our observations demonstrate that plasma interactions with the lunar surface during SEP events, causing extreme surface charging and potentially significant dust electrification and transport, represent an additional hazard associated with space weather.

Conserved charge of a gravity theory with p -form gauge fields and its property under Kaluza-Klein reduction

NASA Astrophysics Data System (ADS)

Peng, Jun-Jin

2017-05-01

In this paper, we investigate the conserved charges of generally diffeomorphism invariant gravity theories with a wide variety of matter fields, particularly of the theories with multiple scalar fields and p -form potentials, in the context of the off-shell generalized Abbott-Deser-Tekin (ADT) formalism. We first construct a new off-shell ADT current that consists of the terms for the variation of a Killing vector and expressions of the field equations as well as the Lie derivative of a surface term with respect to the Killing vector within the framework of generally diffeomorphism invariant gravity theories involving various matter fields. After deriving the off-shell ADT potential corresponding to this current, we propose a formula of conserved charges for these theories. Next, we derive the off-shell ADT potential associated with the generic Lagrangian that describes a large range of gravity theories with a number of scalar fields and p -form potentials. Finally, the properties of the off-shell generalized ADT charges for the theory of Einstein gravity and the gravity theories with a single p -form potential are investigated by performing Kaluza-Klein dimensional reduction along a compactified direction. The results indicate that the charge contributed by all the fields in the lower-dimensional theory is equal to that of the higher-dimensional one at mathematical level with the hypothesis that the higher-dimensional spacetime allows for the existence of the compactified dimension. In order to illustrate our calculations, the mass and angular momentum for the five-dimensional rotating Kaluza-Klein black holes are explicitly evaluated as an example.

Charge and energy minimization in electrical/magnetic stimulation of nervous tissue

NASA Astrophysics Data System (ADS)

Jezernik, Sašo; Sinkjaer, Thomas; Morari, Manfred

2010-08-01

In this work we address the problem of stimulating nervous tissue with the minimal necessary energy at reduced/minimal charge. Charge minimization is related to a valid safety concern (avoidance and reduction of stimulation-induced tissue and electrode damage). Energy minimization plays a role in battery-driven electrical or magnetic stimulation systems (increased lifetime, repetition rates, reduction of power requirements, thermal management). Extensive new theoretical results are derived by employing an optimal control theory framework. These results include derivation of the optimal electrical stimulation waveform for a mixed energy/charge minimization problem, derivation of the charge-balanced energy-minimal electrical stimulation waveform, solutions of a pure charge minimization problem with and without a constraint on the stimulation amplitude, and derivation of the energy-minimal magnetic stimulation waveform. Depending on the set stimulus pulse duration, energy and charge reductions of up to 80% are deemed possible. Results are verified in simulations with an active, mammalian-like nerve fiber model.

Charge and energy minimization in electrical/magnetic stimulation of nervous tissue.

PubMed

Jezernik, Saso; Sinkjaer, Thomas; Morari, Manfred

2010-08-01

In this work we address the problem of stimulating nervous tissue with the minimal necessary energy at reduced/minimal charge. Charge minimization is related to a valid safety concern (avoidance and reduction of stimulation-induced tissue and electrode damage). Energy minimization plays a role in battery-driven electrical or magnetic stimulation systems (increased lifetime, repetition rates, reduction of power requirements, thermal management). Extensive new theoretical results are derived by employing an optimal control theory framework. These results include derivation of the optimal electrical stimulation waveform for a mixed energy/charge minimization problem, derivation of the charge-balanced energy-minimal electrical stimulation waveform, solutions of a pure charge minimization problem with and without a constraint on the stimulation amplitude, and derivation of the energy-minimal magnetic stimulation waveform. Depending on the set stimulus pulse duration, energy and charge reductions of up to 80% are deemed possible. Results are verified in simulations with an active, mammalian-like nerve fiber model.

Charge-Spot Model for Electrostatic Forces in Simulation of Fine Particulates

NASA Technical Reports Server (NTRS)

Walton, Otis R.; Johnson, Scott M.

2010-01-01

The charge-spot technique for modeling the static electric forces acting between charged fine particles entails treating electric charges on individual particles as small sets of discrete point charges, located near their surfaces. This is in contrast to existing models, which assume a single charge per particle. The charge-spot technique more accurately describes the forces, torques, and moments that act on triboelectrically charged particles, especially image-charge forces acting near conducting surfaces. The discrete element method (DEM) simulation uses a truncation range to limit the number of near-neighbor charge spots via a shifted and truncated potential Coulomb interaction. The model can be readily adapted to account for induced dipoles in uncharged particles (and thus dielectrophoretic forces) by allowing two charge spots of opposite signs to be created in response to an external electric field. To account for virtual overlap during contacts, the model can be set to automatically scale down the effective charge in proportion to the amount of virtual overlap of the charge spots. This can be accomplished by mimicking the behavior of two real overlapping spherical charge clouds, or with other approximate forms. The charge-spot method much more closely resembles real non-uniform surface charge distributions that result from tribocharging than simpler approaches, which just assign a single total charge to a particle. With the charge-spot model, a single particle may have a zero net charge, but still have both positive and negative charge spots, which could produce substantial forces on the particle when it is close to other charges, when it is in an external electric field, or when near a conducting surface. Since the charge-spot model can contain any number of charges per particle, can be used with only one or two charge spots per particle for simulating charging from solar wind bombardment, or with several charge spots for simulating triboelectric charging. Adhesive image-charge forces acting on charged particles touching conducting surfaces can be up to 50 times stronger if the charge is located in discrete spots on the particle surface instead of being distributed uniformly over the surface of the particle, as is assumed by most other models. Besides being useful in modeling particulates in space and distant objects, this modeling technique is useful for electrophotography (used in copiers) and in simulating the effects of static charge in the pulmonary delivery of fine dry powders.

Atomistic and molecular effects in electric double layers at high surface charges

DOE PAGES

Templeton, Jeremy Alan; Lee, Jonathan; Mani, Ali

2015-06-16

Here, the Poisson–Boltzmann theory for electrolytes near a charged surface is known to be invalid due to unaccounted physics associated with high ion concentration regimes. In order to investigate this regime, fluids density functional theory (f-DFT) and molecular dynamics (MD) simulations were used to determine electric surface potential as a function of surface charge. Based on these detailed computations, for electrolytes with nonpolar solvent, the surface potential is shown to depend quadratically on the surface charge in the high charge limit. We demonstrate that modified Poisson–Boltzmann theories can model this limit if they are augmented with atomic packing densities providedmore » by MD. However, when the solvent is a highly polar molecule water an intermediate regime is identified in which a constant capacitance is realized. Simulation results demonstrate the mechanism underlying this regime, and for the salt water system studied here, it persists throughout the range of physically realistic surface charge densities so the potential’s quadratic surface charge dependence is not obtained.« less

Effects of organic silicon compounds as additives on charge-discharge cycling efficiencies of lithium in nonaqueous electrolytes for rechargeable lithium cells

NASA Astrophysics Data System (ADS)

Yanagisawa, Ryota; Endo, Hisayuki; Unno, Masafumi; Morimoto, Hideyuki; Tobishima, Shin-ichi

2014-11-01

Influence of mixing organic silicon compounds into 1 M (M: mol L-1) LiPF6-ethylene carbonate (EC)/ethylmethyl carbonate (EMC) (mixing volume ratio = 3:7) mixed solvent electrolytes on charge-discharge cycling efficiencies of lithium metal negative electrodes is examined. As organic silicon compounds, polyether-modified siloxanes with polyethylene oxide chains, chlorotrimethylsilane, tetraethoxysilane, cis-tetra [isobutyl (dimethylsiloxy)] cyclotetrasiloxane and cage-type silsesquioxane are investigated. Charge-discharge cycling tests of lithium are galvanostatically carried out using stainless steel working electrodes. Charge-discharge cycling efficiencies of lithium tend to improve by mixing organic silicon compounds. A cage-type silsesquioxane, octaphenyloctasilsesquioxane (Ph8T8) exhibits the highest cycling efficiency of approximately 80% with small mixing amount of 0.02 M Ph8T8. Mechanism of enhancement of lithium cycling efficiencies by mixing organic silicon compounds is considered to be due to the suppression of excess reduction of LiPF6-EC/EMC by lithium and the growth of surface film on lithium.

Surface charge mapping with a nanopipette.

PubMed

McKelvey, Kim; Kinnear, Sophie L; Perry, David; Momotenko, Dmitry; Unwin, Patrick R

2014-10-01

Nanopipettes are emerging as simple but powerful tools for probing chemistry at the nanoscale. In this contribution the use of nanopipettes for simultaneous surface charge mapping and topographical imaging is demonstrated, using a scanning ion conductance microscopy (SICM) format. When a nanopipette is positioned close to a surface in electrolyte solution, the direct ion current (DC), driven by an applied bias between a quasi-reference counter electrode (QRCE) in the nanopipette and a second QRCE in the bulk solution, is sensitive to surface charge. The charge sensitivity arises because the diffuse double layers at the nanopipette and the surface interact, creating a perm-selective region which becomes increasingly significant at low ionic strengths (10 mM 1:1 aqueous electrolyte herein). This leads to a polarity-dependent ion current and surface-induced rectification as the bias is varied. Using distance-modulated SICM, which induces an alternating ion current component (AC) by periodically modulating the distance between the nanopipette and the surface, the effect of surface charge on the DC and AC is explored and rationalized. The impact of surface charge on the AC phase (with respect to the driving sinusoidal signal) is highlighted in particular; this quantity shows a shift that is highly sensitive to interfacial charge and provides the basis for visualizing charge simultaneously with topography. The studies herein highlight the use of nanopipettes for functional imaging with applications from cell biology to materials characterization where understanding surface charge is of key importance. They also provide a framework for the design of SICM experiments, which may be convoluted by topographical and surface charge effects, especially for small nanopipettes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tewari, Somesh Vinayak, E-mail: somesh-vinayak@yahoo.com, E-mail: svtewari@barc.gov.in; Sharma, Archana; Mittal, K. C.

An experimental investigation of surface flashover characteristics of PMMA and POM is studied in compressed nitrogen gas environment with nitrogen as the background gas. The operating pressure range is from 1kg/cm{sup 2} to 4kg/cm{sup 2}. It is observed that the breakdown voltage of PMMA is higher than POM owing to a higher permittivity mismatch between POM- nitrogen interface as compared to the PMMA- nitrogen interface. The reduction in spacer efficiency with pressure for PMMA is 11% as compared to POM which shows a higher reduction of 18%. This paper further emphasizes on the role of energy level and density ofmore » charge carrier trapping centers for a reduced breakdown voltage in POM as compared to PMMA.« less

High resolution printing of charge

DOEpatents

Rogers, John; Park, Jang-Ung

2015-06-16

Provided are methods of printing a pattern of charge on a substrate surface, such as by electrohydrodynamic (e-jet) printing. The methods relate to providing a nozzle containing a printable fluid, providing a substrate having a substrate surface and generating from the nozzle an ejected printable fluid containing net charge. The ejected printable fluid containing net charge is directed to the substrate surface, wherein the net charge does not substantially degrade and the net charge retained on the substrate surface. Also provided are functional devices made by any of the disclosed methods.

Characterization of the Electrostatic Environment of Launchers

NASA Astrophysics Data System (ADS)

Soyah, Jamila; Mantion, Pascal; Herlem, Yannick

2016-05-01

The purpose of this study was to update knowledge in characterization of the electrostatic environment of launchers in order to be able to propose reductions of design constraints.The first part of this study showed that flashover discharges are the most energetic discharges likely to occur on a launcher. They are mostly due to accumulations of charges by triboelectricity on the external surface of the launcher while flying through clouds containing a lot of small solid particles.Actually flashover discharges are mitigated by limiting the surface's resistance of dielectric materials such as thermal protection set on the external skin of the launcher, thanks to antistatic paints that avoid significant accumulations of charges.But this specified limitation leads to a lot of non- conformances during production phases and, as a result, this leads to additional costs and delays in launches campaigns. That is why on-ground tests have been defined in order to assess the accessibility of a relaxation of those specifications, which would reduce non-conformances.On-ground tests have been carried out, in the second part, on samples of thermal protections covered with antistatic paints with different degraded values of surface resistance. These tests aimed at checking in which conditions a surface discharge can occur in order to deduce a relationship between characteristics of the samples (surface resistance, half-discharge time) and the occurrence of a surface discharge, at ambient pressure and at low pressure.In the third part, in-flight experiments have been defined in order to confirm some hypotheses considered in the study and to assess some parameters in a more accurate way like the incoming charges density per surface unit or the voltage between stages when they get separated, in order to assess more accurately whether the unwinding equalization wire dedicated to maintain the electrostatic balance between stages is necessary or not.

Oxidation and reduction under cover: Chemistry at the confined space between ultra-thin nanoporous silicates and Ru(0001)

DOE Office of Scientific and Technical Information (OSTI.GOV)

J. Anibal Boscoboinik; Zhong, Jian -Qiang; Kestell, John

2016-03-23

The oxidation and reduction of Ru(0001) surfaces at the confined space between two-dimensional nanoporous silica frameworks and Ru(0001) have been investigated using synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS). The porous nature of the frameworks and the weak interaction between the silica and the ruthenium substrate allow oxygen and hydrogen molecules to go through the nanopores and react with the metal at the interface between the silica framework and the metal surface. In this work, three types of two-dimensional silica frameworks have been used to study their influence in the oxidation and reduction of the ruthenium surface at elevated pressuresmore » and temperatures. These frameworks are bilayer silica (0.5 nm thick), bilayer aluminosilicate (0.5 nm thick), and zeolite MFI nanosheets (3 nm thick). It is found that the silica frameworks stay essentially intact under these conditions, but they strongly affect the oxidation of ruthenium, with the 0.5 nm thick aluminosilicate bilayer completely inhibiting the oxidation. Furthermore, the latter is believed to be related to the lower chemisorbed oxygen content arising from electrostatic interactions between the negatively charged aluminosilicate framework and the Ru(0001) substrate.« less

Self-stabilized discharge filament in plane-parallel barrier discharge configuration: formation, breakdown mechanism, and memory effects

NASA Astrophysics Data System (ADS)

Tschiersch, R.; Nemschokmichal, S.; Bogaczyk, M.; Meichsner, J.

2017-10-01

Single self-stabilized discharge filaments were investigated in the plane-parallel electrode configuration. The barrier discharge was operated inside a gap of 3 mm shielded by glass plates to both electrodes, using helium-nitrogen mixtures and a square-wave feeding voltage at a frequency of 2 kHz. The combined application of electrical measurements, ICCD camera imaging, optical emission spectroscopy and surface charge diagnostics via the electro-optic Pockels effect allowed the correlation of the discharge development in the volume and on the dielectric surfaces. The formation criteria and existence regimes were found by systematic variation of the nitrogen admixture to helium, the total pressure and the feeding voltage amplitude. Single self-stabilized discharge filaments can be operated over a wide parameter range, foremost, by significant reduction of the voltage amplitude after the operation in the microdischarge regime. Here, the outstanding importance of the surface charge memory effect on the long-term stability was pointed out by the recalculated spatio-temporally resolved gap voltage. The optical emission revealed discharge characteristics that are partially reminiscent of both the glow-like barrier discharge and the microdischarge regime, such as a Townsend pre-phase, a fast cathode-directed ionization front during the breakdown and radially propagating surface discharges during the afterglow.

Photoelectric charging of partially sunlit dielectric surfaces in space

NASA Technical Reports Server (NTRS)

De, B. R.; Criswell, D. R.

1977-01-01

Sunlight-shadow effects may substantially alter the charging situation for a dielectric surface. The sunlight-shadow boundary tends to be the site of intense multipole electric fields. Charges on a sunlit dielectric surface have a finite effective mobility. The charge distribution tends to resemble that on a conducting surface. A boundary between a conducting and a dielectric surface may not represent a conductivity discontinuity when this boundary is sunlit; charges may migrate at a nontrivial rate across the boundary. A contracting or expanding sunlit area may experience a supercharging.

Effect of the surface charge discretization on electric double layers: a Monte Carlo simulation study.

PubMed

Madurga, Sergio; Martín-Molina, Alberto; Vilaseca, Eudald; Mas, Francesc; Quesada-Pérez, Manuel

2007-06-21

The structure of the electric double layer in contact with discrete and continuously charged planar surfaces is studied within the framework of the primitive model through Monte Carlo simulations. Three different discretization models are considered together with the case of uniform distribution. The effect of discreteness is analyzed in terms of charge density profiles. For point surface groups, a complete equivalence with the situation of uniformly distributed charge is found if profiles are exclusively analyzed as a function of the distance to the charged surface. However, some differences are observed moving parallel to the surface. Significant discrepancies with approaches that do not account for discreteness are reported if charge sites of finite size placed on the surface are considered.

Luminescent systems based on the isolation of conjugated PI systems and edge charge compensation with polar molecules on a charged nanostructured surface

DOEpatents

Ivanov, Ilia N.; Puretzky, Alexander A.; Zhao, Bin; Geohegan, David B.; Styers-Barnett, David J.; Hu, Hui

2014-07-15

A photoluminescent or electroluminescent system and method of making a non-luminescent nanostructured material into such a luminescent system is presented. The method of preparing the luminescent system, generally, comprises the steps of modifying the surface of a nanostructured material to create isolated regions to act as luminescent centers and to create a charge imbalance on the surface; applying more than one polar molecule to the charged surface of the nanostructured material; and orienting the polar molecules to compensate for the charge imbalance on the surface of the nanostructured material. The compensation of the surface charge imbalance by the polar molecules allows the isolated regions to exhibit luminescence.

Characterization of the surface charge distribution on kaolinite particles using high resolution atomic force microscopy

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Zhao, Cunlu; Klaassen, Aram; van den Ende, Dirk; Mugele, Frieder; Siretanu, Igor

2016-02-01

Most solid surfaces, in particular clay minerals and rock surfaces, acquire a surface charge upon exposure to an aqueous environment due to adsorption and/or desorption of ionic species. Macroscopic techniques such as titration and electrokinetic measurements are commonly used to determine the surface charge and ζ -potential of these surfaces. However, because of the macroscopic averaging character these techniques cannot do justice to the role of local heterogeneities on the surfaces. In this work, we use dynamic atomic force microscopy (AFM) to determine the distribution of surface charge on the two (gibbsite-like and silica-like) basal planes of kaolinite nanoparticles immersed in aqueous electrolyte with a lateral resolution of approximately 30 nm. The surface charge density is extracted from force-distance curves using DLVO theory in combination with surface complexation modeling. While the gibbsite-like and the silica-like facet display on average positive and negative surface charge values as expected, our measurements reveal lateral variations of more than a factor of two on seemingly atomically smooth terraces, even if high resolution AFM images clearly reveal the atomic lattice on the surface. These results suggest that simple surface complexation models of clays that attribute a unique surface chemistry and hence homogeneous surface charge densities to basal planes may miss important aspects of real clay surfaces.

Investigating the reversibility of structural modifications of Li xNi yMn zCo 1-y-zO₂ cathode materials during initial charge/discharge, at multiple length scales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hwang, Sooyeon; Bak, Seong -Min; Kim, Seung Min

2015-08-11

In this work, we investigate the structural modifications occurring at the bulk, subsurface, and surface scales of Li xNi yMn zCo 1-y-zO₂ (NMC; y, z = 0.8, 0.1 and 0.4, 0.3, respectively) cathode materials during the initial charge/discharge. Various analytical tools, such as X-ray diffraction, selected-area electron diffraction, electron energy-loss spectroscopy, and high-resolution electron microscopy, are used to examine the structural properties of the NMC cathode materials at the three different scales. Cut-off voltages of 4.3 and 4.8 V are applied during the electrochemical tests as the normal and extreme conditions, respectively. The high-Ni-content NMC cathode materials exhibit unusual behaviors,more » which is deviate from the general redox reactions during the charge or discharge. The transition metal (TM) ions in the high-Ni-content NMC cathode materials, which are mostly Ni ions, are reduced at 4.8 V, even though TMs are usually oxidized to maintain charge neutrality upon the removal of Li. It was found that any changes in the crystallographic and electronic structures are mostly reversible down to the sub-surface scale, despite the unexpected reduction of Ni ions. However, after the discharge, traces of the phase transitions remain at the edges of the NMC cathode materials at the scale of a few nanometers (i.e., surface scale). This study demonstrates that the structural modifications in NMC cathode materials are induced by charge as well as discharge at multiple length scales. These changes are nearly reversible after the first cycle, except at the edges of the samples, which should be avoided because these highly localized changes can initiate battery degradation.« less

Special raster scanning for reduction of charging effects in scanning electron microscopy.

PubMed

Suzuki, Kazuhiko; Oho, Eisaku

2014-01-01

A special raster scanning (SRS) method for reduction of charging effects is developed for the field of SEM. Both a conventional fast scan (horizontal direction) and an unusual scan (vertical direction) are adopted for acquiring raw data consisting of many sub-images. These data are converted to a proper SEM image using digital image processing techniques. About sharpness of the image and reduction of charging effects, the SRS is compared with the conventional fast scan (with frame-averaging) and the conventional slow scan. Experimental results show the effectiveness of SRS images. By a successful combination of the proposed scanning method and low accelerating voltage (LV)-SEMs, it is expected that higher-quality SEM images can be more easily acquired by the considerable reduction of charging effects, while maintaining the resolution. © 2013 Wiley Periodicals, Inc.

Proximity charge sensing for semiconductor detectors

DOEpatents

Luke, Paul N; Tindall, Craig S; Amman, Mark

2013-10-08

A non-contact charge sensor includes a semiconductor detector having a first surface and an opposing second surface. The detector includes a high resistivity electrode layer on the first surface and a low resistivity electrode on the high resistivity electrode layer. A portion of the low resistivity first surface electrode is deleted to expose the high resistivity electrode layer in a portion of the area. A low resistivity electrode layer is disposed on the second surface of the semiconductor detector. A voltage applied between the first surface low resistivity electrode and the second surface low resistivity electrode causes a free charge to drift toward the first or second surface according to a polarity of the free charge and the voltage. A charge sensitive preamplifier coupled to a non-contact electrode disposed at a distance from the exposed high resistivity electrode layer outputs a signal in response to movement of free charge within the detector.

Direct Synthetic Control over the Size, Composition, and Photocatalytic Activity of Octahedral Copper Oxide Materials: Correlation Between Surface Structure and Catalytic Functionality.

PubMed

Nguyen, Michelle A; Bedford, Nicholas M; Ren, Yang; Zahran, Elsayed M; Goodin, Robert C; Chagani, Fatima F; Bachas, Leonidas G; Knecht, Marc R

2015-06-24

We report a synthetic approach to form octahedral Cu2O microcrystals with a tunable edge length and demonstrate their use as catalysts for the photodegradation of aromatic organic compounds. In this particular study, the effects of the Cu(2+) and reductant concentrations and stoichiometric ratios were carefully examined to identify their roles in controlling the final material composition and size under sustainable reaction conditions. Varying the ratio and concentrations of Cu(2+) and reductant added during the synthesis determined the final morphology and composition of the structures. Octahedral particles were prepared at selected Cu(2+):glucose ratios that demonstrated a range of photocatalytic reactivity. The results indicate that material composition, surface area, and substrate charge effects play important roles in controlling the overall reaction rate. In addition, analysis of the post-reacted materials revealed photocorrosion was inhibited and that surface etching had preferentially occurred at the particle edges during the reaction, suggesting that the reaction predominately occurred at these interfaces. Such results advance the understanding of how size and composition affect the surface interface and catalytic functionality of materials.

Electrochromic Graphene Molecules

DOE PAGES

Ji, Zhiqiang; Doorn, Stephen K.; Sykora, Milan

2015-03-13

Polyclic aromatic hydrocarbons, also called Graphene Molecules (GMs), with chemical composition C 132H 36(COOH) 2 were synthesized in-situ on the surface of transparent nanocrystaline indium tin oxide (nc-ITO) electrodes. Their electronic structure was studied electrochemically and spectro-electrochemically. Variations in the potential applied onto the nc-ITO/GM electrodes induce only small changes in the observed current but they produce dramatic changes in the absorption of the GMs, which are associated with their oxidation and reduction. Analysis of the absorption changes using modified Nernst equation is used to determine standard potentials associated with the individual charge transfer processes. For the GMs prepared heremore » these were found to be E 1,ox 0 = 0.77± 0.01 V and E 2,ox 0 = 1.24 ± 0.02 V vs. NHE for the first and second oxidation and E 1,red 0 = -1.50 ± 0.04 V for the first reduction. The charge transfer processes are found to be non-ideal. The non-ideality factors associated with the oxidation and reduction processes suggest presence of strong interactions between the GM redox centers. Under the conditions of potential cycling GMs show rapid (seconds) color change with high contrast and stability. An electrochromic application is demonstrated wherein the GMs are used as the optically active component.« less

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy

PubMed Central

2017-01-01

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl2 concentration. Using DLVO theory with charge regulation, we determine from the measured force–distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca2+ ion adsorption, while Cl– adsorption at higher CaCl2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl– ions will co-adsorb, thereby changing the observed ordered surface structure. PMID:29140711

Probing the Surface Charge on the Basal Planes of Kaolinite Particles with High-Resolution Atomic Force Microscopy.

PubMed

Kumar, N; Andersson, M P; van den Ende, D; Mugele, F; Siretanu, I

2017-12-19

High-resolution atomic force microscopy is used to map the surface charge on the basal planes of kaolinite nanoparticles in an ambient solution of variable pH and NaCl or CaCl 2 concentration. Using DLVO theory with charge regulation, we determine from the measured force-distance curves the surface charge distribution on both the silica-like and the gibbsite-like basal plane of the kaolinite particles. We observe that both basal planes do carry charge that varies with pH and salt concentration. The silica facet was found to be negatively charged at pH 4 and above, whereas the gibbsite facet is positively charged at pH below 7 and negatively charged at pH above 7. Investigations in CaCl 2 at pH 6 show that the surface charge on the gibbsite facet increases for concentration up to 10 mM CaCl 2 and starts to decrease upon further increasing the salt concentration to 50 mM. The increase of surface charge at low concentration is explained by Ca 2+ ion adsorption, while Cl - adsorption at higher CaCl 2 concentrations partially neutralizes the surface charge. Atomic resolution imaging and density functional theory calculations corroborate these observations. They show that hydrated Ca 2+ ions can spontaneously adsorb on the gibbsite facet of the kaolinite particle and form ordered surface structures, while at higher concentrations Cl - ions will co-adsorb, thereby changing the observed ordered surface structure.

The decolouration of methyl orange using aluminum foam, ultrasound and direct electric current

NASA Astrophysics Data System (ADS)

Liu, C. M.; Huang, X. Y.; Zhang, H. Y.; Dai, J. D.; Ning, C. C.

2018-01-01

The decolouration of methyl orange (MO) using aluminum (Al) foam, ultrasound and direct electric current (DC) is investigated. The decolouration rate (DR) of MO using only Al foam is low because there is a passivation oxide layer on the Al foam surface. Due to the low utilization of ultrasound in MO water solution medium, the DR of MO using only ultrasonic irradiation is also poor. The DR of MO is greatly increased when Al foam, ultrasonic irradiation and DC are used together. There is good synergistic effect between Al foam, ultrasound and DC in decolouration of MO. This enhancement of DR may be related to the cavitation, cleaning of Al foam surface and water electrolysis. Due to the surface charge on wire carrying stationary current, Al foam with DC acts like a serious anodes and cathodes and makes water electrolysis giving hydrogen gas to cleavage azo bond. The DC applied on Al foam is beneficial for reductive decolouration of MO. Our results show that DC is a new way for the reductive decolouration MO in water.

Enhanced photocatalytic CO2 reduction to CH4 over separated dual co-catalysts Au and RuO2

NASA Astrophysics Data System (ADS)

Dong, Chunyang; Hu, Songchang; Xing, Mingyang; Zhang, Jinlong

2018-04-01

A spatially separated, dual co-catalyst photocatalytic system was constructed by the stepwise introduction of RuO2 and Au nanoparticles (NPs) at the internal and external surfaces of a three dimensional, hierarchically ordered TiO2-SiO2 (HTSO) framework (the final photocatalyst was denoted as Au/HRTSO). Characterization by HR-TEM, EDS-mapping, XRD and XPS confirmed the existence and spatially separated locations of Au and RuO2. In CO2 photocatalytic reduction (CO2PR), Au/HRTSO (0.8%) shows the optimal performance in both the activity and selectivity towards CH4; the CH4 yield is almost twice that of the singular Au/HTSO or HRTSO (0.8%, weight percentage of RuO2) counterparts. Generally, Au NPs at the external surface act as electron trapping agents and RuO2 NPs at the inner surface act as hole collectors. This advanced spatial configuration could promote charge separation and transfer efficiency, leading to enhanced CO2PR performance in both the yield and selectivity toward CH4 under simulated solar light irradiation.

Determination of the mechanism and extent of surface degradation in Ni-based cathode materials after repeated electrochemical cycling

NASA Astrophysics Data System (ADS)

Hwang, Sooyeon; Kim, Se Young; Chung, Kyung Yoon; Stach, Eric A.; Kim, Seung Min; Chang, Wonyoung

2016-09-01

We take advantage of scanning transmission electron microscopy and electron energy loss spectroscopy to investigate the changes in near-surface electronic structure and quantify the degree of local degradation of Ni-based cathode materials with the layered structure (LiNi0.8Mn0.1Co0.1O2 and LiNi0.4Mn0.3Co0.3O2) after 20 cycles of delithiation and lithiation. Reduction of transition metals occurs in the near-surface region of cathode materials: Mn is the major element to be reduced in the case of relatively Mn-rich composition, while reduction of Ni ions is dominant in Ni-rich materials. The valences of Ni and Mn ions are complementary, i.e., when one is reduced, the other is oxidized in order to maintain charge neutrality. The depth of degradation zone is found to be much deeper in Ni-rich materials. This comparative analysis provides important insights needed for the devising of new cathode materials with high capacity as well as long lifetime.

Electronically shielded solid state charged particle detector

DOEpatents

Balmer, D.K.; Haverty, T.W.; Nordin, C.W.; Tyree, W.H.

1996-08-20

An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite. 1 fig.

Electronically shielded solid state charged particle detector

DOEpatents

Balmer, David K.; Haverty, Thomas W.; Nordin, Carl W.; Tyree, William H.

1996-08-20

An electronically shielded solid state charged particle detector system having enhanced radio frequency interference immunity includes a detector housing with a detector entrance opening for receiving the charged particles. A charged particle detector having an active surface is disposed within the housing. The active surface faces toward the detector entrance opening for providing electrical signals representative of the received charged particles when the received charged particles are applied to the active surface. A conductive layer is disposed upon the active surface. In a preferred embodiment, a nonconductive layer is disposed between the conductive layer and the active surface. The conductive layer is electrically coupled to the detector housing to provide a substantially continuous conductive electrical shield surrounding the active surface. The inner surface of the detector housing is supplemented with a radio frequency absorbing material such as ferrite.

Leaching of manganese from electrolytic manganese residue by electro-reduction.

PubMed

Shu, Jiancheng; Liu, Renlong; Liu, Zuohua; Chen, Hongliang; Tao, Changyuan

2017-08-01

In this study, an improved process for leaching manganese from electrolytic manganese residue (EMR) by electro-reduction was developed. The mechanisms of the electro-reduction leaching were investigated through X-ray diffraction, scanning electron microscopy, X-ray fluorescence, and Brunauer Emmett Teller. The results show that the electric field could change the surface charge distribution of EMR particles, and the high-valent manganese can be reduced by electric field. The leaching efficient of manganese reached 84.1% under the optimal leaching condition: 9.2 wt% H 2 SO 4 , current density of 25 mA/cm 2 , solid-to-liquid ratio of 1:5, and leaching time for 1 h. It is 37.9% higher than that attained without an electric field. Meanwhile, the manganese content in EMR decreased from 2.57% to 0.48%.

Interface passivation and trap reduction via hydrogen fluoride for molybdenum disulfide on silicon oxide back-gate transistors

NASA Astrophysics Data System (ADS)

Hu, Yaoqiao; San Yip, Pak; Tang, Chak Wah; Lau, Kei May; Li, Qiang

2018-04-01

Layered semiconductor molybdenum disulfide (MoS2) has recently emerged as a promising material for flexible electronic and optoelectronic devices because of its finite bandgap and high degree of gate control. Here, we report a hydrogen fluoride (HF) passivation technique for improving the carrier mobility and interface quality of chemical vapor deposited monolayer MoS2 on a SiO2/Si substrate. After passivation, the fabricated MoS2 back-gate transistors demonstrate a more than double improvement in average electron mobility, a reduced gate hysteresis gap of 3 V, and a low interface trapped charge density of ˜5.8 × 1011 cm-2. The improvements are attributed to the satisfied interface dangling bonds, thus a reduction of interface trap states and trapped charges. Surface x-ray photoelectron spectroscopy analysis and first-principles simulation were performed to verify the HF passivation effect. The results here highlight the necessity of a MoS2/dielectric passivation strategy and provides a viable route for enhancing the performance of MoS2 nano-electronic devices.

Strong coupling electrostatics for randomly charged surfaces: antifragility and effective interactions.

PubMed

Ghodrat, Malihe; Naji, Ali; Komaie-Moghaddam, Haniyeh; Podgornik, Rudolf

2015-05-07

We study the effective interaction mediated by strongly coupled Coulomb fluids between dielectric surfaces carrying quenched, random monopolar charges with equal mean and variance, both when the Coulomb fluid consists only of mobile multivalent counterions and when it consists of an asymmetric ionic mixture containing multivalent and monovalent (salt) ions in equilibrium with an aqueous bulk reservoir. We analyze the consequences that follow from the interplay between surface charge disorder, dielectric and salt image effects, and the strong electrostatic coupling that results from multivalent counterions on the distribution of these ions and the effective interaction pressure they mediate between the surfaces. In a dielectrically homogeneous system, we show that the multivalent counterions are attracted towards the surfaces with a singular, disorder-induced potential that diverges logarithmically on approach to the surfaces, creating a singular but integrable counterion density profile that exhibits an algebraic divergence at the surfaces with an exponent that depends on the surface charge (disorder) variance. This effect drives the system towards a state of lower thermal 'disorder', one that can be described by a renormalized temperature, exhibiting thus a remarkable antifragility. In the presence of an interfacial dielectric discontinuity, the singular behavior of counterion density at the surfaces is removed but multivalent counterions are still accumulated much more strongly close to randomly charged surfaces as compared with uniformly charged ones. The interaction pressure acting on the surfaces displays in general a highly non-monotonic behavior as a function of the inter-surface separation with a prominent regime of attraction at small to intermediate separations. This attraction is caused directly by the combined effects from charge disorder and strong coupling electrostatics of multivalent counterions, which dominate the surface-surface repulsion due to the (equal) mean charges on the two surfaces and the osmotic pressure of monovalent ions residing between them. These effects can be quite significant even with a small degree of surface charge disorder relative to the mean surface charge. The strong coupling, disorder-induced attraction is typically much stronger than the van der Waals interaction between the surfaces, especially within a range of several nanometers for the inter-surface separation, where such effects are predicted to be most pronounced.

Reductions of E. coli, echovirus type 12 and bacteriophages in an intermittently operated household-scale slow sand filter.

PubMed

Elliott, M A; Stauber, C E; Koksal, F; DiGiano, F A; Sobsey, M D

2008-05-01

Point-of-use (POU) drinking water treatment technology enables those without access to safe water sources to improve the quality of their water by treating it in the home. One of the most promising emerging POU technologies is the biosand filter (BSF), a household-scale, intermittently operated slow sand filter. Over 500,000 people in developing countries currently use the filters to treat their drinking water. However, despite this successful implementation, there has been almost no systematic, process engineering research to substantiate the effectiveness of the BSF or to optimize its design and operation. The major objectives of this research were to: (1) gain an understanding of the hydraulic flow condition within the filter (2) characterize the ability of the BSF to reduce the concentration of enteric bacteria and viruses in water and (3) gain insight into the key parameters of filter operation and their effects on filter performance. Three 6-8 week microbial challenge experiments are reported herein in which local surface water was seeded with E. coli, echovirus type 12 and bacteriophages (MS2 and PRD-1) and charged to the filter daily. Tracer tests indicate that the BSF operated at hydraulic conditions closely resembling plug flow. The performance of the filter in reducing microbial concentrations was highly dependent upon (1) filter ripening over weeks of operation and (2) the daily volume charged to the filter. BSF performance was best when less than one pore volume (18.3-L in the filter design studied) was charged to the filter per day and this has important implications for filter design and operation. Enhanced filter performance due to ripening was generally observed after roughly 30 days. Reductions of E. coli B ranged from 0.3 log10 (50%) to 4 log10, with geometric mean reductions after at least 30 days of operation of 1.9 log10. Echovirus 12 reductions were comparable to those for E. coli B with a range of 1 log10 to >3 log10 and mean reductions after 30 days of 2.1 log10. Bacteriophage reductions were much lower, ranging from zero to 1.3 log10 (95%) with mean reductions of only 0.5 log10 (70%). These data indicate that virus reduction by BSF may differ substantially depending upon the specific viral agent.

Effect of surface material on electrostatic charging of houseflies (Musca domestica L).

PubMed

McGonigle, Daniel F; Jackson, Chris W

2002-04-01

Houseflies (Musca domestica L) accumulated electrostatic charges when walking over clean, uncharged dielectric surfaces. The charges elicited on a walking housefly by a range of materials were quantified, allowing a triboelectric series to be determined relative to M domestica. This ranged from surfaces that charged individuals positively, e.g. Correx (corrugated polypropylene) [.1 (+/- 4.2)pC], to those that applied a negative charge, e.g. clear cast acrylic [-14.9 (+/- 2.9)pC]. Maximum positive and negative charges accumulated by individual M domestica were +73 and -27 pC. Replicate measurements on the same fly and surface showed little variation. Variation between individuals was not related to sex and was not consistent between surfaces. Different materials charged M domestica significantly differently and individual flies had significantly different charging properties. Variation in temperature between 21.3 degrees C and 24.7 degrees C and humidity between 24% and 41% RH significantly affected charge accumulated by M domestica on some surfaces, although further experimentation is needed to confirm this. The implications of this work are discussed in relation to insect trap design and pollination biology.

Adhesion and inactivation of Gram-negative and Gram-positive bacteria on photoreactive TiO2/polymer and Ag-TiO2/polymer nanohybrid films

NASA Astrophysics Data System (ADS)

Tallósy, Szabolcs Péter; Janovák, László; Nagy, Elisabeth; Deák, Ágota; Juhász, Ádám; Csapó, Edit; Buzás, Norbert; Dékány, Imre

2016-05-01

The aim of this study was to develop photoreactive surface coatings, possessing antibacterial properties and can be activated under visible light illumination (λmax = 405 nm) using LED-light source. The photocatalytically active titanium dioxide (TiO2) was functionalized with silver nanoparticles (Ag NPs) and immobilized in polyacrylate based nanohybrid thin film in order to facilitate visible light activity (λAg/TiO2,max = 500 nm). First, the photocatalytic activity was modelled by following ethanol vapor degradation. The plasmonic functionalization resulted in 15% enhancement of the activity compared to pure TiO2. The photoreactive antimicrobial (5 log reduction of cfu in 2 h) surface coatings are able to inactivate clinically relevant pathogen strains (methicillin resistant Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa) within short time (60-120 min) due to the formed and quantified reactive oxygen species (ROS). The existence of electrostatic interactions between the negatively charged bacteria (from -0.89 to -3.19 μeq/109 cfu) and positively charged photocatalyst particles (in the range of +0.38 and +12.3 meq/100 g) was also proven by charge titration measurements. The surface inactivation of the bacteria and the photocatalytic degradation of the cell wall component were also confirmed by fluorescence and transmission electron microscopic observations, respectively. According to the results an effective sterilizing system and prevention strategy can be developed and carried out against dangerous microorganisms in health care.

Carbon Dots as Versatile Photosensitizers for Solar-Driven Catalysis with Redox Enzymes.

PubMed

Hutton, Georgina A M; Reuillard, Bertrand; Martindale, Benjamin C M; Caputo, Christine A; Lockwood, Colin W J; Butt, Julea N; Reisner, Erwin

2016-12-28

Light-driven enzymatic catalysis is enabled by the productive coupling of a protein to a photosensitizer. Photosensitizers used in such hybrid systems are typically costly, toxic, and/or fragile, with limited chemical versatility. Carbon dots (CDs) are low-cost, nanosized light-harvesters that are attractive photosensitizers for biological systems as they are water-soluble, photostable, nontoxic, and their surface chemistry can be easily modified. We demonstrate here that CDs act as excellent light-absorbers in two semibiological photosynthetic systems utilizing either a fumarate reductase (FccA) for the solar-driven hydrogenation of fumarate to succinate or a hydrogenase (H 2 ase) for reduction of protons to H 2 . The tunable surface chemistry of the CDs was exploited to synthesize positively charged ammonium-terminated CDs (CD-NHMe 2 + ), which were capable of transferring photoexcited electrons directly to the negatively charged enzymes with high efficiency and stability. Enzyme-based turnover numbers of 6000 mol succinate (mol FccA) -1 and 43,000 mol H 2 (mol H 2 ase) -1 were reached after 24 h. Negatively charged carboxylate-terminated CDs (CD-CO 2 - ) displayed little or no activity, and the electrostatic interactions at the CD-enzyme interface were determined to be essential to the high photocatalytic activity observed with CD-NHMe 2 + . The modular surface chemistry of CDs together with their photostability and aqueous solubility make CDs versatile photosensitizers for redox enzymes with great scope for their utilization in photobiocatalysis.

Interfacial Energy Alignment at the ITO/Ultra-Thin Electron Selective Dielectric Layer Interface and Its Effect on the Efficiency of Bulk-Heterojunction Organic Solar Cells.

PubMed

Itoh, Eiji; Goto, Yoshinori; Saka, Yusuke; Fukuda, Katsutoshi

2016-04-01

We have investigated the photovoltaic properties of an inverted bulk heterojunction (BHJ) cell in a device with an indium-tin-oxide (ITO)/electron selective layer (ESL)/P3HT:PCBM active layer/MoOx/Ag multilayered structure. The insertion of only single layer of poly(diallyl-dimethyl-ammonium chloride) (PDDA) cationic polymer film (or poly(ethyleneimine) (PEI) polymeric interfacial dipole layer) and titanium oxide nanosheet (TN) films as an ESL effectively improved cell performance. Abnormal S-shaped curves were observed in the inverted BHJ cells owing to the contact resistance across the ITO/active layer interface and the ITO/PDDA/TN/active layer interface. The series resistance across the ITO/ESL interface in the inverted BHJ cell was successfully reduced using an interfacial layer with a positively charged surface potential with respect to ITO base electrode. The positive dipole in PEI and the electronic charge phenomena at the electrophoretic deposited TN (ED-TN) films on ITO contributed to the reduction of the contact resistance at the electrode interface. The surface potential measurement revealed that the energy alignment by the transfer of electronic charges from the ED-TN to the base electrodes. The insertion of the ESL with a large positive surface potential reduced the potential barrier for the electron injection at ITO/TN interface and it improved the photovoltaic properties of the inverted cell with an ITO/TN/active layer/MoOx/Ag structure.

Photoinduced Charge Transfer from Titania to Surface Doping Site

PubMed Central

Inerbaev, Talgat; Hoefelmeyer, James D.; Kilin, Dmitri S.

2013-01-01

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting. PMID:23795229

Photoinduced Charge Transfer from Titania to Surface Doping Site.

PubMed

Inerbaev, Talgat; Hoefelmeyer, James D; Kilin, Dmitri S

2013-05-16

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO 2 . Charge transfer from the photo-excited TiO 2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO 2 nanorod and catalytic site. A slab of TiO 2 represents a fragment of TiO 2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO 2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO 2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting.

Oil Contact Angles in a Water-Decane-Silicon Dioxide System: Effects of Surface Charge

NASA Astrophysics Data System (ADS)

Xu, Shijing; Wang, Jingyao; Wu, Jiazhong; Liu, Qingjie; Sun, Chengzhen; Bai, Bofeng

2018-04-01

Oil wettability in the water-oil-rock systems is very sensitive to the evolution of surface charges on the rock surfaces induced by the adsorption of ions and other chemical agents in water flooding. Through a set of large-scale molecular dynamics simulations, we reveal the effects of surface charge on the oil contact angles in an ideal water-decane-silicon dioxide system. The results show that the contact angles of oil nano-droplets have a great dependence on the surface charges. As the surface charge density exceeds a critical value of 0.992 e/nm2, the contact angle reaches up to 78.8° and the water-wet state is very apparent. The variation of contact angles can be confirmed from the number density distributions of oil molecules. With increasing the surface charge density, the adsorption of oil molecules weakens and the contact areas between nano-droplets and silicon dioxide surface are reduced. In addition, the number density distributions, RDF distributions, and molecular orientations indicate that the oil molecules are adsorbed on the silicon dioxide surface layer-by-layer with an orientation parallel to the surface. However, the layered structure of oil molecules near the silicon dioxide surface becomes more and more obscure at higher surface charge densities.

Oil Contact Angles in a Water-Decane-Silicon Dioxide System: Effects of Surface Charge.

PubMed

Xu, Shijing; Wang, Jingyao; Wu, Jiazhong; Liu, Qingjie; Sun, Chengzhen; Bai, Bofeng

2018-04-19

Oil wettability in the water-oil-rock systems is very sensitive to the evolution of surface charges on the rock surfaces induced by the adsorption of ions and other chemical agents in water flooding. Through a set of large-scale molecular dynamics simulations, we reveal the effects of surface charge on the oil contact angles in an ideal water-decane-silicon dioxide system. The results show that the contact angles of oil nano-droplets have a great dependence on the surface charges. As the surface charge density exceeds a critical value of 0.992 e/nm 2 , the contact angle reaches up to 78.8° and the water-wet state is very apparent. The variation of contact angles can be confirmed from the number density distributions of oil molecules. With increasing the surface charge density, the adsorption of oil molecules weakens and the contact areas between nano-droplets and silicon dioxide surface are reduced. In addition, the number density distributions, RDF distributions, and molecular orientations indicate that the oil molecules are adsorbed on the silicon dioxide surface layer-by-layer with an orientation parallel to the surface. However, the layered structure of oil molecules near the silicon dioxide surface becomes more and more obscure at higher surface charge densities.

Prediction of purification of biopharmeceuticals with molecular dynamics

NASA Astrophysics Data System (ADS)

Ustach, Vincent; Faller, Roland

Purification of biopharmeceuticals remains the most expensive part of protein-based drug production. In ion exchange chromatography (IEX), prediction of the elution ionic strength of host cell and target proteins has the potential to reduce the parameter space for scale-up of protein production. The complex shape and charge distribution of proteins and pores complicates predictions of the interactions in these systems. All-atom molecular dynamics methods are beyond the scope of computational limits for mass transport regimes. We present a coarse-grained model for proteins for prediction of elution pH and ionic strength. By extending the raspberry model for colloid particles to surface shapes and charge distributions of proteins, we can reproduce the behavior of proteins in IEX. The average charge states of titratatable amino acid residues at relevant pH values are determined by extrapolation from all-atom molecular dynamics at pH 7. The pH specific all-atom electrostatic field is then mapped onto the coarse-grained surface beads of the raspberry particle. The hydrodynamics are reproduced with the lattice-Boltzmann scheme. This combination of methods allows very long simulation times. The model is being validated for known elution procedures by comparing the data with experiments. Defense Threat Reduction Agency (Grant Number HDTRA1-15-1-0054).

Understanding performance limitation and suppression of leakage current or self-discharge in electrochemical capacitors: a review.

PubMed

Ike, Innocent S; Sigalas, Iakovos; Iyuke, Sunny

2016-01-14

Self-discharge is known to have considerable adverse effects on the performance and application of electrochemical capacitors (ECs). Thus, obtaining an understanding of EC self-discharge mechanism(s) and subsequent derivation and solution of EC models, subject to a particular mechanism or combination of mechanisms during charging, discharging and storage of the device, is the only way to solve problems associated with EC self-discharge. In this review, we summarize recent progress with respect to EC self-discharge by considering the two basic types, electric double-layer capacitors (EDLC) and pseudocapacitors, and their hybrids with their respective charge storage mechanisms, distinguishable self-discharge mechanisms, charge redistribution and charge/energy loss during self-discharge. It was clearly observed that most of the voltage reduction is not purely due to the self-discharge effect but is basically due to redistribution of charge carriers deep inside pores and can therefore be retrieved from a capacitor during long-time discharging. Tuning the self-discharge rate is therefore feasible for single-walled carbon nanotube (SWNT) ECs and can be achieved by simply adjusting the surface chemistry of the nanotubes. The effects of surface chemistry modification on EC self-discharge are very important in studying and suppressing the self-discharge process and will benefit potential applications of ECs with respect to energy retention. Self-discharge can be averted by the use of redox couples that are transformed to insoluble species via electrolysis and adsorbed onto the activated carbon electrode in redox-couple EDLCs, thus transforming the EDLC electrolyte into a material that can store charge. Self-discharge in ECs can also be successfully suppressed by utilizing an ion-interchange layer (ion-exchange membrane), separator or CuSO4 mobile electrolyte that can be converted into an insoluble species by electrolysis during the charge/discharge process. This will help in producing a modern-day blueprint for ECs with high capacitance and improved energy sustainability.

Critical Dipole Length for the Wetting Transition Due to Collective Water-dipoles Interactions

PubMed Central

Wang, Chunlei; Zhou, Bo; Tu, Yusong; Duan, Manyi; Xiu, Peng; Li, Jingye; Fang, Haiping

2012-01-01

The wetting behavior of water on the solid surfaces is fundamental to various physical, chemical and biological processes. Conventionally, the surface with charges or charge dipoles is hydrophilic, whereas the non-polar surface is hydrophobic though some exceptions were recently reported. Using molecular dynamics simulations, we show that there is a critical length of the charge dipoles on the solid surface. The solid surface still exhibited hydrophobic behavior when the dipole length was less than the critical value, indicating that the water molecules on the solid surface seemed not “feel” attractive interactions from the charge dipoles on the solid surface. Those unexpected observations result from the collective interactions between the water molecules and charge dipoles on the solid surface, where the steric exclusion effect between water molecules greatly reduces the water-dipole interactions. Remarkably, the steric exclusion effect is also important for surfaces with charge dipole lengths greater than this critical length. PMID:22496954

Polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent counterions: A Monte Carlo simulation study

NASA Astrophysics Data System (ADS)

Luque-Caballero, Germán; Martín-Molina, Alberto; Quesada-Pérez, Manuel

2014-05-01

Both experiments and theory have evidenced that multivalent cations can mediate the interaction between negatively charged polyelectrolytes and like-charged objects, such as anionic lipoplexes (DNA-cation-anionic liposome complexes). In this paper, we use Monte Carlo simulations to study the electrostatic interaction responsible for the trivalent-counterion-mediated adsorption of polyelectrolytes onto a like-charged planar surface. The evaluation of the Helmholtz free energy allows us to characterize both the magnitude and the range of the interaction as a function of the polyelectrolyte charge, surface charge density, [3:1] electrolyte concentration, and cation size. Both polyelectrolyte and surface charge favor the adsorption. It should be stressed, however, that the adsorption will be negligible if the surface charge density does not exceed a threshold value. The effect of the [3:1] electrolyte concentration has also been analyzed. In certain range of concentrations, the counterion-mediated attraction seems to be independent of this parameter, whereas very high concentrations of salt weaken the adsorption. If the trivalent cation diameter is doubled the adsorption moderates due to the excluded volume effects. The analysis of the integrated charge density and ionic distributions suggests that a delicate balance between charge inversion and screening effects governs the polyelectrolyte adsorption onto like-charged surfaces mediated by trivalent cations.

Controlling Gas-Phase Reactions for Efficient Charge Reduction Electrospray Mass Spectrometry of Intact Proteins

PubMed Central

Frey, Brian L.; Lin, Yuan; Westphall, Michael S.; Smith, Lloyd M.

2006-01-01

Charge reduction electrospray mass spectrometry (CREMS) reduces the charge states of electrospray-generated ions, which concentrates the ions from a protein into fewer peaks spread over a larger m/z range, thereby increasing peak separation and decreasing spectral congestion. An optimized design for a CREMS source is described that provides an order-of-magnitude increase in sensitivity compared to previous designs and provides control over the extent of charge reduction. Either a corona discharge or an α-particle source was employed to generate anions that abstract protons from electrosprayed protein cations. These desired ion/ion proton transfer reactions predominated, but some oxidation and ion-attachment reactions also occurred leading to new peaks or mass-shifted broader peaks while decreasing signal intensity. The species producing these deleterious side-reactions were identified, and conditions were found that prevented their formation. Spectrometer m/z biases were examined because of their effect upon the signal intensity of higher m/z charge-reduced protein ions. The utility of this atmospheric pressure CREMS was demonstrated using a cell lysate fraction from E. coli. The spectral simplification afforded by CREMS reveals more proteins than are observed without charge reduction. PMID:16198118

Charge renormalization and inversion of a highly charged lipid bilayer: effects of dielectric discontinuities and charge correlations.

PubMed

Taheri-Araghi, Sattar; Ha, Bae-Yeun

2005-08-01

We reexamine the problem of charge renormalization and inversion of a highly charged surface of a low dielectric constant immersed in ionic solutions. To be specific, we consider an asymmetrically charged lipid bilayer, in which only one layer is negatively charged. In particular, we study how dielectric discontinuities and charge correlations (among lipid charges and condensed counterions) influence the effective charge of the surface. When counterions are monovalent (e.g., Na+), our mean-field approach implies that dielectric discontinuities can enhance counterion condensation. A simple scaling picture shows how the effects of dielectric discontinuities and surface-charge distributions are intertwined: Dielectric discontinuities diminish condensation if the backbone charge is uniformly smeared out while counterions are localized in space; they can, however, enhance condensation when the backbone charge is discrete. In the presence of asymmetric salts such as CaCl2 , we find that the correlation effect, treated at the Gaussian level, is more pronounced when the surface has a lower dielectric constant, inverting the sign of the charge at a smaller value of Ca2+ concentration.

Spin Uncoupling in Chemisorbed OCCO and CO 2: Two High-Energy Intermediates in Catalytic CO 2 Reduction

DOE PAGES

Hedstrom, Svante; dos Santos, Egon Campos; Liu, Chang; ...

2018-05-08

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an averagemore » gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 – quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.« less

Ion association at discretely-charged dielectric interfaces: Giant charge inversion [Dielectric response controlled ion association at physically heterogeneous surfaces: Giant charge reversal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhi -Yong; Wu, Jianzhong

2017-07-11

Giant charge reversal has been identified for the first time by Monte Carlo simulation for a discretely charged surface in contact with a trivalent electrolyte solution. It takes place regardless of the surface charge density under study and the monovalent salt. In stark contrast to earlier predictions based on the 2-dimensional Wigner crystal model to describe strong correlation of counterions at the macroion surface, we find that giant charge reversal reflects an intricate interplay of ionic volume effects, electrostatic correlations, surface charge heterogeneity, and the dielectric response of the confined fluids. While the novel phenomenon is yet to be confirmedmore » with experiment, the simulation results appear in excellent agreement with a wide range of existing observations in the subregime of charge inversion. Lastly, our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.« less

Triboelectric, Corona, and Induction Charging of Insulators as a Function of Pressure

NASA Technical Reports Server (NTRS)

Hogue, Michael D.; Mucciolo, Eduardo R.; Calle, Carlos I.

2006-01-01

Theoretical and experimental research has been performed that shows that the surface charge on an insulator after triboelectric charging with another insulator is rapidly dissipated with lowered atmospheric pressure. This pressure discharge is consistent with surface ions being evaporated off the surface once their vapor pressure is attained. In this paper we will report on the results of three different charging techniques (triboelectric, corona, and induction) performed on selected polymers with varying atmospheric pressure. This data will show that ion exchange between the polymer samples is the mechanism responsible for most of the surface charge on the polymer surfaces.

An integrated electrolysis - electrospray - ionization antimicrobial platform using Engineered Water Nanostructures (EWNS) for food safety applications.

PubMed

Vaze, Nachiket; Jiang, Yi; Mena, Lucas; Zhang, Yipei; Bello, Dhimiter; Leonard, Stephen S; Morris, Anna M; Eleftheriadou, Mary; Pyrgiotakis, Georgios; Demokritou, Philip

2018-03-01

Engineered water nanostructures (EWNS) synthesized utilizing electrospray and ionization of water, have been, recently, shown to be an effective, green, antimicrobial platform for surface and air disinfection, where reactive oxygen species (ROS), generated and encapsulated within the particles during synthesis, were found to be the main inactivation mechanism. Herein, the antimicrobial potency of the EWNS was further enhanced by integrating electrolysis, electrospray and ionization of de-ionized water in the EWNS synthesis process. Detailed physicochemical characterization of these enhanced EWNS (eEWNS) was performed using state-of-the-art analytical methods and has shown that, while both size and charge remain similar to the EWNS (mean diameter of 13 nm and charge of 13 electrons), they possess a three times higher ROS content. The increase of the ROS content as a result of the addition of the electrolysis step before electrospray and ionization led to an increased antimicrobial ability as verified by E. coli inactivation studies using stainless steel coupons. It was shown that a 45-minute exposure to eEWNS resulted in a 4-log reduction as opposed to a 1.9-log reduction when exposed to EWNS. In addition, the eEWNS were assessed for their potency to inactivate natural microbiota (total viable and yeast and mold counts), as well as, inoculated E.coli on the surface of fresh organic blackberries. The results showed a 97% (1.5-log) inactivation of the total viable count, a 99% (2-log) reduction in the yeast and mold count and a 2.5-log reduction of the inoculated E.coli after 45 minutes of exposure, without any visual changes to the fruit. This enhanced antimicrobial activity further underpins the EWNS platform as an effective, dry and chemical free approach suitable for a variety of food safety applications and could be ideal for delicate fresh produce that cannot withstand the classical, wet disinfection treatments.

Ultrafast dynamics of colloidal semiconductor nanocrystals relevant to solar fuels production

NASA Astrophysics Data System (ADS)

Cogan, Nicole M. B.; Liu, Cunming; Qiu, Fen; Burke, Rebeckah; Krauss, Todd D.

2017-05-01

Artificial conversion of sunlight to chemical fuels has attracted attention for several decades as a potential source of clean, renewable energy. We recently found that CdSe quantum dots (QDs) and simple aqueous Ni2+ salts in the presence of a sacrificial electron donor form a highly efficient, active, and robust system for photochemical reduction of protons to molecular hydrogen. Ultrafast transient absorption spectroscopy studies of electron transfer (ET) processes from the QDs to the Ni catalysts reveal extremely fast ET, and provide a fundamental explanation for the exceptional photocatalytic H2 activity. Additionally, by studying H2 production of the Ni catalyst with CdSe/CdS nanoparticles of various structures, it was determined that surface charge density plays an important role in charge transfer and ultimately H2 production activity.

InN/GaN quantum dot superlattices: Charge-carrier states and surface electronic structure

NASA Astrophysics Data System (ADS)

Kanouni, F.; Brezini, A.; Djenane, M.; Zou, Q.

2018-03-01

We have theoretically investigated the electron energy spectra and surface states energy in the three dimensionally ordered quantum dot superlattices (QDSLs) made of InN and GaN semiconductors. The QDSL is assumed in this model to be a matrix of GaN containing cubic dots of InN of the same size and uniformly distributed. For the miniband’s structure calculation, the resolution of the effective mass Schrödinger equation is done by decoupling it in the three directions within the framework of Kronig-Penney model. We found that the electrons minibands in infinite ODSLs are clearly different from those in the conventional quantum-well superlattices. The electrons localization and charge-carrier states are very dependent on the quasicrystallographic directions, the size and the shape of the dots which play a role of the artificial atoms in such QD supracrystal. The energy spectrum of the electron states localized at the surface of InN/GaN QDSL is represented by Kronig-Penney like-model, calculated via direct matching procedure. The calculation results show that the substrate breaks symmetrical shape of QDSL on which some localized electronic surface states can be produced in minigap regions. Furthermore, we have noticed that the surface states degeneracy is achieved in like very thin bands located in the minigaps, identified by different quantum numbers nx, ny, nz. Moreover, the surface energy bands split due to the reduction of the symmetry of the QDSL in z-direction.

Electric Double-Layer Interaction between Dissimilar Charge-Conserved Conducting Plates.

PubMed

Chan, Derek Y C

2015-09-15

Small metallic particles used in forming nanostructured to impart novel optical, catalytic, or tribo-rheological can be modeled as conducting particles with equipotential surfaces that carry a net surface charge. The value of the surface potential will vary with the separation between interacting particles, and in the absence of charge-transfer or electrochemical reactions across the particle surface, the total charge of each particle must also remain constant. These two physical conditions require the electrostatic boundary condition for metallic nanoparticles to satisfy an equipotential whole-of-particle charge conservation constraint that has not been studied previously. This constraint gives rise to a global charge conserved constant potential boundary condition that results in multibody effects in the electric double-layer interaction that are either absent or are very small in the familiar constant potential or constant charge or surface electrochemical equilibrium condition.

Photoinduced charge carriers' accumulation and its impact on random lasing in Nd3+ doped (Pb,La)(Zr,Ti)O3 ceramics

NASA Astrophysics Data System (ADS)

Xu, Caixia; Zhang, Jingwen; Xu, Long; Ma, Xinyan; Zhao, Hua

2017-06-01

To pinpoint the driving forces behind the random lasing in Nd3+ doped lanthanum lead zirconate titanate (Nd:PLZT) ceramic plates, a combinatorial cavity with two gain media (Nd:YVO4 and Nd:PLZT) was used to study the switching feature between conventional lasing and random lasing oscillations. The complex laser output dynamics observed hinted that the photo-induced charge accumulation on the plate surface and the grain boundaries of Nd:PLZT is responsible for the lasing action switching, which was confirmed by a series of experiments, including strong electro-induced scattering, remarkable photoinduced currents, and light transmission reduction, along with measured single-pass-gain over the theoretical limit. It was found that the charge accumulation results in optical energy storage and nonuniform refractive index and hence strong scattering, which give rise to the random walks and weak localization of photons and long lasting lasing action and mode switching.

Self-assembled hierarchical direct Z-scheme g-C3N4/ZnO microspheres with enhanced photocatalytic CO2 reduction performance

NASA Astrophysics Data System (ADS)

Nie, Ning; Zhang, Liuyang; Fu, Junwei; Cheng, Bei; Yu, Jiaguo

2018-05-01

Photocatalytic reduction of CO2 into hydrocarbon fuels has been regarded as a promising approach to ease the greenhouse effect and the energy shortage. Herein, an electrostatic self-assembly method was exploited to prepare g-C3N4/ZnO composite microsphere. This method simply utilized the opposite surface charge of each component, achieving a hierarchical structure with intimate contact between them. A much improved photocatalytic CO2 reduction activity was attained. The CH3OH production rate was 1.32 μmol h-1 g-1, which was 2.1 and 4.1 times more than that of the pristine ZnO and g-C3N4, respectively. This facile design bestowed the g-C3N4/ZnO composite an extended light adsorption caused by multi-light scattering effect. It also guaranteed the uniform distribution of g-C3N4 nanosheets on the surface of ZnO microspheres, maximizing their advantage and synergistic effect. Most importantly, the preeminent performance was proposed and validated based on the direct Z-scheme. The recombination rate was considerably suppressed. This work features the meliority of constructing hierarchical direct Z-scheme structures in photocatalytic CO2 reduction reactions.

Charging of moving surfaces by corona discharges sustained in air

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jun-Chieh, E-mail: junchwan@umich.edu; Kushner, Mark J., E-mail: mjkush@umich.edu; Zhang, Daihua, E-mail: dhzhang@tju.edu.cn

Atmospheric pressure corona discharges are used in electrophotographic (EP) printing technologies for charging imaging surfaces such as photoconductors. A typical corona discharge consists of a wire (or wire array) biased with a few hundred volts of dc plus a few kV of ac voltage. An electric discharge is produced around the corona wire from which electrons drift towards and charge the underlying dielectric surface. The surface charging reduces the voltage drop across the gap between the corona wire and the dielectric surface, which then terminates the discharge, as in a dielectric barrier discharge. In printing applications, this underlying surface ismore » continuously moving throughout the charging process. For example, previously charged surfaces, which had reduced the local electric field and terminated the local discharge, are translated out of the field of view and are replaced with uncharged surface. The uncharged surface produces a rebound in the electric field in the vicinity of the corona wire which in turn results in re-ignition of the discharge. The discharge, so reignited, is then asymmetric. We found that in the idealized corona charging system we investigated, a negatively dc biased corona blade with a dielectric covered ground electrode, the discharge is initially sustained by electron impact ionization from the bulk plasma and then dominated by ionization from sheath accelerated secondary electrons. Depending on the speed of the underlying surface, the periodic re-ignition of the discharge can produce an oscillatory charging pattern on the moving surface.« less

Adsorption of insulin peptide on charged single-walled carbon nanotubes: significant role of ordered water molecules.

PubMed

Shen, Jia-Wei; Wu, Tao; Wang, Qi; Kang, Yu; Chen, Xin

2009-06-02

Ordered hydration shells: The more ordered hydration shells outside the charged CNT surfaces prevent more compact adsorption of the peptide in the charged CNT systems [picture: see text], but peptide binding strengths on the charged CNT surfaces are stronger due to the electrostatic interaction.Studies of adsorption dynamics and stability for peptides/proteins on single-walled carbon nanotubes (SWNTs) are of great importance for a better understanding of the properties and nature of nanotube-based biosystems. Herein, the dynamics and mechanism of the adsorption of the insulin chain B peptide on different charged SWNTs are investigated by explicit solvent molecular dynamics simulations. The results show that all types of surfaces effectively attract the model peptide. Water molecules play a significant role in peptide adsorption on the surfaces of charged carbon nanotubes (CNTs). Compared to peptide adsorption on neutral CNT surfaces, the more ordered hydration shells outside the tube prevent more compact adsorption of the peptide in charged CNT systems. This shield effect leads to a smaller conformational change and van der Waals interaction between the peptide and surfaces, but peptide binding strengths on charged CNT surfaces are stronger than those on the neutral CNT surface due to the strong electrostatic interaction. The result of these simulations implies the possibility of improving the binding strength of peptides/proteins on CNT surfaces, as well as keeping the integrity of the peptide/protein conformation in peptide/protein-CNT complexes by charging the CNTs.

Effect of surface charge density on the affinity of oxide nanoparticles for the vapor-water interface.

PubMed

Brown, Matthew A; Duyckaerts, Nicolas; Redondo, Amaia Beloqui; Jordan, Inga; Nolting, Frithjof; Kleibert, Armin; Ammann, Markus; Wörner, Hans Jakob; van Bokhoven, Jeroen A; Abbas, Zareen

2013-04-23

Using in-situ X-ray photoelectron spectroscopy at the vapor-water interface, the affinity of nanometer-sized silica colloids to adsorb at the interface is shown to depend on colloid surface charge density. In aqueous suspensions at pH 10 corrected Debye-Hückel theory for surface complexation calculations predict that smaller silica colloids have increased negative surface charge density that originates from enhanced screening of deprotonated silanol groups (≡Si-O(-)) by counterions in the condensed ion layer. The increased negative surface charge density results in an electrostatic repulsion from the vapor-water interface that is seen to a lesser extent for larger particles that have a reduced charge density in the XPS measurements. We compare the results and interpretation of the in-situ XPS and corrected Debye-Hückel theory for surface complexation calculations with traditional surface tension measurements. Our results show that controlling the surface charge density of colloid particles can regulate their adsorption to the interface between two dielectrics.

Study of Pellets and Lumps as Raw Materials in Silicon Production from Quartz and Silicon Carbide

NASA Astrophysics Data System (ADS)

Dal Martello, E.; Tranell, G.; Gaal, S.; Raaness, O. S.; Tang, K.; Arnberg, L.

2011-10-01

The use of high-purity carbon and quartz raw materials reduces the need for comprehensive refining steps after the silicon has been produced carbothermically in the electric reduction furnace. The current work aims at comparing the reaction mechanisms and kinetics occurring in the inner part of the reduction furnace when pellets or lumpy charge is used, as well as the effect of the raw material mix. Laboratory-scale carbothermic reduction experiments have been carried out in an induction furnace. High-purity silicon carbide and two different high-purity hydrothermal quartzes were charged as raw materials at different molar ratios. The charge was in the form of lumps (size, 2-5 mm) or as powder (size, 10-20 μm), mixed and agglomerated as pellets (size, 1-3 mm) and reacted at 2273 K (2000 °C). The thermal properties of the quartzes were measured also by heating a small piece of quartz in CO atmosphere. The investigated quartzes have different reactivity in reducing atmosphere. The carbothermal reduction experiments show differences in the reacted charge between pellets and lumps as charge material. Solid-gas reactions take place from the inside of the pellets porosity, whereas reactions in lumps occur topochemically. Silicon in pellets is produced mainly in the rim zone. Larger volumes of silicon have been found when using lumpy charge. More SiO is produced when using pellets than for lumpy SiO2 for the same molar ratio and heating conditions. The two SiC polytypes used in the carbothermal reduction experiments as carbon reductants presented different reactivity.

Detection of subsurface core-level shifts in Si 2p core-level photoemission from Si(111)-(1x1):As

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paggel, J.J.; Hasselblatt, M.; Horn, K.

1997-04-01

The (7 x 7) reconstruction of the Si(111) surface arises from a lowering energy through the reduction of the number of dangling bonds. This reconstruction can be removed by the adsorption of atoms such as hydrogen which saturate the dangling bonds, or by the incorporation of atoms, such as arsenic which, because of the additional electron it possesses, can form three bonds and a nonreactive lone pair orbital from the remaining two electrons. Core and valence level photoemission and ion scattering data have shown that the As atoms replace the top silicon atoms. Previous core level spectra were interpreted inmore » terms of a bulk and a single surface doublet. The authors present results demonstrate that the core level spectrum contains two more lines. The authors assign these to subsurface silicon layers which also experience changes in the charge distribution when a silicon atom is replaced by an arsenic atom. Subsurface core level shifts are not unexpected since the modifications of the electronic structure and/or of photohole screening are likely to decay into the bulk and not just to affect the top-most substrate atoms. The detection of subsurface components suggests that the adsorption of arsenic leads to charge flow also in the second double layer of the Si(111) surface. In view of the difference in atomic radius between As and Si, it was suggested that the (1 x 1): As surface is strained. The presence of charge rearrangement up to the second double layer implies that the atomic coordinates also exhibit deviations from their ideal Si(111) counterparts, which might be detected through a LEED I/V or photoelectron diffraction analysis.« less

Fragmentation of organic ions bearing fixed multiple charges observed in MALDI MS.

PubMed

Lou, Xianwen; Li, Bao; de Waal, Bas F M; Schill, Jurgen; Baker, Matthew B; Bovee, Ralf A A; van Dongen, Joost L J; Milroy, Lech-Gustav; Meijer, E W

2018-01-01

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS) was used to analyze a series of synthetic organic ions bearing fixed multiple charges. Despite the multiple intrinsic charges, only singly charged ions were recorded in each case. In addition to the pseudo-molecular ions formed by counterion adduction, deprotonation and electron capture, a number of fragment ions were also observed. Charge splitting by fragmentation was found to be a viable route for charge reduction leading to the formation of the observed singly charged fragment ions. Unlike multivalent metal ions, organic ions can rearrange and/or fragment during charge reduction. This fragmentation process will evidently complicate the interpretation of the MALDI MS spectrum. Because MALDI MS is usually considered as a soft ionization technique, the fragment ion peaks can easily be erroneously interpreted as impurities. Therefore, the awareness and understanding of the underlying MALDI-induced fragmentation pathways is essential for a proper interpretation of the corresponding mass spectra. Due to the fragment ions generated during charge reduction, special care should be taken in the MALDI MS analysis of multiply charged ions. In this work, the possible mechanisms by which the organic ions bearing fixed multiple charges fragment are investigated. With an improved understanding of the fragmentation mechanisms, MALDI TOF MS should still be a useful technique for the characterization of organic ions with fixed multiple charges. Copyright © 2017 John Wiley & Sons, Ltd.

Mechanism of the free charge carrier generation in the dielectric breakdown

NASA Astrophysics Data System (ADS)

Rahim, N. A. A.; Ranom, R.; Zainuddin, H.

2017-12-01

Many studies have been conducted to investigate the effect of environmental, mechanical and electrical stresses on insulator. However, studies on physical process of discharge phenomenon, leading to the breakdown of the insulator surface are lacking and difficult to comprehend. Therefore, this paper analysed charge carrier generation mechanism that can cause free charge carrier generation, leading toward surface discharge development. Besides, this paper developed a model of surface discharge based on the charge generation mechanism on the outdoor insulator. Nernst’s Planck theory was used in order to model the behaviour of the charge carriers while Poisson’s equation was used to determine the distribution of electric field on insulator surface. In the modelling of surface discharge on the outdoor insulator, electric field dependent molecular ionization was used as the charge generation mechanism. A mathematical model of the surface discharge was solved using method of line technique (MOL). The result from the mathematical model showed that the behaviour of net space charge density was correlated with the electric field distribution.

Salt-Driven Deposition of Thermoresponsive Polymer-Coated Metal Nanoparticles on Solid Substrates.

PubMed

Zhang, Zhiyue; Maji, Samarendra; da Fonseca Antunes, André B; De Rycke, Riet; Hoogenboom, Richard; De Geest, Bruno G

2016-06-13

Here we report on a simple, generally applicable method for depositing metal nanoparticles on a wide variety of solid surfaces under all aqueous conditions. Noble-metal nanoparticles obtained by citrate reduction followed by coating with thermoresponsive polymers spontaneously form a monolayer-like structure on a wide variety of substrates in presence of sodium chloride whereas this phenomenon does not occur in salt-free medium. Interestingly, this phenomenon occurs below the cloud point temperature of the polymers and we hypothesize that salt ion-induced screening of electrostatic charges on the nanoparticle surface entropically favors hydrophobic association between the polymer-coated nanoparticles and a hydrophobic substrate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Collisional charging of individual submillimeter particles: Using ultrasonic levitation to initiate and track charge transfer

NASA Astrophysics Data System (ADS)

Lee, Victor; James, Nicole M.; Waitukaitis, Scott R.; Jaeger, Heinrich M.

2018-03-01

Electrostatic charging of insulating fine particles can be responsible for numerous phenomena ranging from lightning in volcanic plumes to dust explosions. However, even basic aspects of how fine particles become charged are still unclear. Studying particle charging is challenging because it usually involves the complexities associated with many-particle collisions. To address these issues, we introduce a method based on acoustic levitation, which makes it possible to initiate sequences of repeated collisions of a single submillimeter particle with a flat plate, and to precisely measure the particle charge in situ after each collision. We show that collisional charge transfer between insulators is dependent on the hydrophobicity of the contacting surfaces. We use glass, which we modify by attaching nonpolar molecules to the particle, the plate, or both. We find that hydrophilic surfaces develop significant positive charges after contacting hydrophobic surfaces. Moreover, we demonstrate that charging between a hydrophilic and a hydrophobic surface is suppressed in an acidic environment and enhanced in a basic one. Application of an electric field during each collision is found to modify the charge transfer, again depending on surface hydrophobicity. We discuss these results within the context of contact charging due to ion transfer, and we show that they lend strong support to O H- ions as the charge carriers.

A Combined Model of Charging of the Surface and Bulk of a Dielectric Target by Electrons with the Energies 10-30 keV

NASA Astrophysics Data System (ADS)

Zykov, V. M.; Neiman, D. A.

2018-04-01

A physico-mathematical model of the processes of radiation-induced charging of dielectric materials with open surfaces, irradiated with monoenergetic electrons in the energy range 10-30 keV, is described. The model takes into account the relationship between the processes of surface and bulk charging for the given conditions of the experimental design, which accounts for the effect of anomalously long charging of dielectrics after the incident energy of primary electrons during charging is reduced to below the second critical energy for the secondary electronic emission coefficient. The initial fast phase of charging a high-resistivity dielectric material (Al2O3) is investigated. It is shown that as the incident electron energy is approaching the second critical energy during charging, the secondary electronic emission is partially suppressed due to negative charging of the open surface of the dielectric and formation of a near-surface inversion electrical field retarding the electronic emission yield.

Nylon surface modification: 2. Nylon-supported composite films.

PubMed

Herrera-Alonso, Margarita; McCarthy, Thomas J; Jia, Xinqiao

2006-02-14

We have developed techniques for the introduction of reactive functional groups to nylon surfaces via site-specific reactions targeting at the naturally abundant amide repeating units on the surface. In this report, we describe the fabrication of nylon-supported composite surfaces using the most efficient modification methods we have developed. N-Alkylation with (3-glycidoxypropyl)triethoxysilane (GPTES) in the presence of potassium tert-butoxide (t-BuOK) leads to surfaces with silica-like reactivity. Subsequent chemical vapor deposition using tetrachlorosilane (SiCl4) and water results in composite films with a thin layer of silica, which was made hydrophobic by reaction with a fluorinated silane reagent. Reduction of the amide groups with borane-THF (BH3-THF) complex leads to a 69% conversion of surface amides to the corresponding secondary amine groups. Alginate was chosen as the model polyelectrolyte for the introduction of a hydrated surface layer. Because of the strong electrostatic interaction between alginate and the amine-enriched nylon surfaces, the adsorption is fast and concentration-independent (within the concentration range studied). The polysaccharide coats the surface homogeneously, without the formation of large aggregates. The amine surfaces obtained by reduction with BH3-THF ((BH3-THF)nylon-NH) and by alkylation with 2-bromoethylamine hydrobromide (BEA-HBr, (EBA-HBr)nylon-NH2) were also used to study gold deposition through electroless plating. Immobilization of a negatively charged metal complex (AuCl4(-)) was achieved through electrostatic interaction. Gold particles disperse preferentially in the bulk of (EBA-HBr)nylon-NH2 films, while they remain confined to the outer surface layer of (BH3-THF)nylon-NH films.

Ion association at discretely-charged dielectric interfaces: Giant charge inversion

NASA Astrophysics Data System (ADS)

Wang, Zhi-Yong; Wu, Jianzhong

2017-07-01

Giant charge reversal has been identified for the first time by Monte Carlo simulation for a discretely charged surface in contact with a trivalent electrolyte solution. It takes place regardless of the surface charge density under study and the monovalent salt. In stark contrast to earlier predictions based on the 2-dimensional Wigner crystal model to describe strong correlation of counterions at the macroion surface, we find that giant charge reversal reflects an intricate interplay of ionic volume effects, electrostatic correlations, surface charge heterogeneity, and the dielectric response of the confined fluids. While the novel phenomenon is yet to be confirmed with experiment, the simulation results appear in excellent agreement with a wide range of existing observations in the subregime of charge inversion. Our findings may have far-reaching implications to understanding complex electrochemical phenomena entailing ionic fluids under dielectric confinements.

VARIABLE CHARGE SOILS: MINERALOGY AND CHEMISTRY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Ranst, Eric; Qafoku, Nikolla; Noble, Andrew

2016-09-19

Soils rich in particles with amphoteric surface properties in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders (1) are considered to be variable charge soils (2) (Table 1). The term “variable charge” is used to describe organic and inorganic soil constituents with reactive surface groups whose charge varies with pH and ionic concentration and composition of the soil solution. Such groups are the surface carboxyl, phenolic and amino functional groups of organic materials in soils, and surface hydroxyl groups of Fe and Al oxides, allophane and imogolite. The hydroxyl surface groups are also present on edges of some phyllosilicate mineralsmore » such as kaolinite, mica, and hydroxyl-interlayered vermiculite. The variable charge is developed on the surface groups as a result of adsorption or desorption of ions that are constituents of the solid phase, i.e., H+, and the adsorption or desorption of solid-unlike ions that are not constituents of the solid phase. Highly weathered soils and subsoils (e.g., Oxisols and some Ultisols, Alfisols and Andisols) may undergo isoelectric weathering and reach a “zero net charge” stage during their development. They usually have a slightly acidic to acidic soil solution pH, which is close to either the point of zero net charge (PZNC) (3) or the point of zero salt effect (PZSE) (3). They are characterized by high abundances of minerals with a point of zero net proton charge (PZNPC) (3) at neutral and slightly basic pHs; the most important being Fe and Al oxides and allophane. Under acidic conditions, the surfaces of these minerals are net positively charged. In contrast, the surfaces of permanent charge phyllosilicates are negatively charged regardless of ambient conditions. Variable charge soils therefore, are heterogeneous charge systems.« less

Water organization between oppositely charged surfaces: Implications for protein sliding along DNA a)

NASA Astrophysics Data System (ADS)

Marcovitz, Amir; Naftaly, Aviv; Levy, Yaakov

2015-02-01

Water molecules are abundant in protein-DNA interfaces, especially in their nonspecific complexes. In this study, we investigated the organization and energetics of the interfacial water by simplifying the geometries of the proteins and the DNA to represent them as two equally and oppositely charged planar surfaces immersed in water. We found that the potential of mean force for bringing the two parallel surfaces into close proximity comprises energetic barriers whose properties strongly depend on the charge density of the surfaces. We demonstrated how the organization of the water molecules into discretized layers and the corresponding energetic barriers to dehydration can be modulated by the charge density on the surfaces, salt, and the structure of the surfaces. The 1-2 layers of ordered water are tightly bound to the charged surfaces representing the nonspecific protein-DNA complex. This suggests that water might mediate one-dimensional diffusion of proteins along DNA (sliding) by screening attractive electrostatic interactions between the positively charged molecular surface on the protein and the negatively charged DNA backbone and, in doing so, reduce intermolecular friction in a manner that smoothens the energetic landscape for sliding, and facilitates the 1D diffusion of the protein.

Characterizing the effects of regolith surface roughness on photoemission from surfaces in space

NASA Astrophysics Data System (ADS)

Dove, A.; Horanyi, M.; Wang, X.

2017-12-01

Surfaces of airless bodies and spacecraft in space are exposed to a variety of charging environments. A balance of currents due to plasma bombardment, photoemission, electron and ion emission and collection, and secondary electron emission determines the surface's charge. Photoelectron emission is the dominant charging process on sunlit surfaces in the inner solar system due to the intense solar UV radiation. This can result in a net positive surface potential, with a cloud of photoelectrons immediately above the surface, called the photoelectron sheath. Conversely, the unlit side of the body will charge negatively due the collection of the fast-moving solar wind electrons. The interaction of charged dust grains with these positively and negatively charged surfaces, and within the photoelectron and plasma sheaths may explain the occurrence of dust lofting, levitation and transport above the lunar surface. The surface potential of exposed objects is also dependent on the material properties of their surfaces. Composition and particle size primarily affect the quantum efficiency of photoelectron generation; however, surface roughness can also control the charging process. In order to characterize these effects, we have conducted laboratory experiments to examine the role of surface roughness in generating photoelectrons in dedicated laboratory experiments using solid and dusty surfaces of the same composition (CeO2), and initial comparisons with JSC-1 lunar simulant. Using Langmuir probe measurements, we explore the measured potentials above insulating surfaces exposed to UV and an electric field, and we show that the photoemission current from a dusty surface is largely reduced due to its higher surface roughness, which causes a significant fraction of the emitted photoelectrons to be re-absorbed within the surface. We will discuss these results in context of similar situations on planetary surfaces.

Space and surface charge behavior analysis of charge-eliminated polymer films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Oda, Tetsuji; Takashima, Kazunori; Ichiyama, Shinichiro

1995-12-31

Charge behavior of corona-charged or charge eliminated polymer films being dipped in the city water were studied. They were polytetrafluoroethylene (PTFE teflon{trademark}), polypropylene (PP), low density or high density polyethylene (LDPE or HDPE) thin films which are as grown (native) or plasma-processed. The plasma processing at low pressure was tested as antistatic processing. Charge elimination was done by being dipped in alcohol or city water. TSDC analysis and surface charge profile measurement were done for both charged and charge eliminated polymer films. Surface charge density of plasma processed polymer films just after corona charging is roughly the same as thatmore » of an original film. There is little difference between surface charge density profile of a native film and that of a plasma processed film. A large hetero current peak of TSDC was observed at room temperature for a processed film. It was found that the hetero peak disappears after charge elimination process. A pressure pulse wave method by using a pulse-driven piezoelectric PVDF polymer film as a piezoelectric actuator was newly developed to observe real space charge distribution. A little difference of internal space charge distribution between the plasma processed film and the native one after corona charging is found.« less

Facile synthesis of highly active reduced graphene oxide-CuI catalyst through a simple combustion method for photocatalytic reduction of CO2 to methanol

NASA Astrophysics Data System (ADS)

Zhang, Wenjun; Li, Yingjie; Zhang, Xiaoxiong; Li, Cuiluo

2017-09-01

We report a facile combustion method synthesis of reduced graphene oxide/CuI composites as a photocatalyst, in which CuI nanoparticles were homogeneously distributed on the surface of reduced graphene oxide (rGO), showing a good visible light response. The rGO-supported and unsupported CuI hybrids were tested over the photocatalytic reduction of CO2 for methanol evolution in visible light. In the current study rGO-CuI composites have shown excellent yields (19.91 μmol g-cat-1). rGO provides a light-weight, charge complementary and two-dimensional material that interacts effectively with the CuI nanoparticles.

Dual path mechanism in the thermal reduction of graphene oxide.

PubMed

Larciprete, Rosanna; Fabris, Stefano; Sun, Tao; Lacovig, Paolo; Baraldi, Alessandro; Lizzit, Silvano

2011-11-02

Graphene is easily produced by thermally reducing graphene oxide. However, defect formation in the C network during deoxygenation compromises the charge carrier mobility in the reduced material. Understanding the mechanisms of the thermal reactions is essential for defining alternative routes able to limit the density of defects generated by carbon evolution. Here, we identify a dual path mechanism in the thermal reduction of graphene oxide driven by the oxygen coverage: at low surface density, the O atoms adsorbed as epoxy groups evolve as O(2) leaving the C network unmodified. At higher coverage, the formation of other O-containing species opens competing reaction channels, which consume the C backbone. We combined spectroscopic tools and ab initio calculations to probe the species residing on the surface and those released in the gas phase during heating and to identify reaction pathways and rate-limiting steps. Our results illuminate the current puzzling scenario of the low temperature gasification of graphene oxide.

Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy.

PubMed

Chen, Xiaoyun; Wang, Jie; Paszti, Zoltan; Wang, Fulin; Schrauben, Joel N; Tarabara, Volodymyr V; Schmaier, Alvin H; Chen, Zhan

2007-05-01

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), zeta-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules.

Experimental and Theoretical Investigations of Glass Surface Charging Phenomena

NASA Astrophysics Data System (ADS)

Agnello, Gabriel

Charging behavior of multi-component display-type (i.e. low alkali) glass surfaces has been studied using a combination of experimental and theoretical methods. Data obtained by way of a Rolling Sphere Test (RST), streaming/zeta potential and surface energy measurements from commercially available display glass surfaces (Corning EAGLE XGRTM and Lotus(TM) XT) suggest that charge accumulation is highly dependent on surface treatment (chemical and/or physical modification) and measurement environment, presumably through reactionary mechanisms at the surface with atmospheric moisture. It has been hypothesized that water dissociation, along with the corresponding hydroxylation of the glass surface, are important processes related to charging in glass-metal contact systems. Classical Molecular Dynamics (MD) simulations, in conjunction with various laboratory based measurements (RST, a newly developed ElectroStatic Gauge (ESG) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)) on simpler Calcium AluminoSilicate (CAS) glass surfaces were used to further explore these phenomena. Analysis of simulated high-silica content (≥50%) (CAS) glass structures suggest that controlled variation of bulk chemistry can directly affect surface defect concentrations, such as non-bridging oxygen (NBO), which can be suitable high-energy sites for hydrolysis-type reactions to occur. Calculated NBO surface concentrations correlate well with charge based measurements on laboratory fabricated CAS surfaces. The data suggest that a directional/polar shift in contact-charge transfer occurs at low silica content (≤50%) where the highest concentrations of NBOs are observed. Surface charging sensitivity with respect to NBO concentration decreases as the relative humidity of the measurement environment increases; which should be expected as the highly reactive sites are progressively covered by liquid water layers. DRIFTS analysis of CAS powders expand on this analysis showing a gradual increase in molecular water absorption at the surface in samples containing ≥60% silica, and an abrupt decrease in those with ≤60% silica. This behavior is very likely related to the aforementioned charge polarity shift (negative (-) to positive (+)) in low silica containing glasses, leading to the conclusion that structural defect mediated charge accumulation and/or transfer are likely to be important mechanisms related to the contact charging of glass surfaces.

Electrically Controllable Microparticle Synthesis and Digital Microfluidic Manipulation by Electric-Field-Induced Droplet Dispensing into Immiscible Fluids

PubMed Central

Um, Taewoong; Hong, Jiwoo; Im, Do Jin; Lee, Sang Joon; Kang, In Seok

2016-01-01

The dispensing of tiny droplets is a basic and crucial process in a myriad of applications, such as DNA/protein microarray, cell cultures, chemical synthesis of microparticles, and digital microfluidics. This work systematically demonstrates droplet dispensing into immiscible fluids through electric charge concentration (ECC) method. It exhibits three main modes (i.e., attaching, uniform, and bursting modes) as a function of flow rates, applied voltages, and gap distances between the nozzle and the oil surface. Through a conventional nozzle with diameter of a few millimeters, charged droplets with volumes ranging from a few μL to a few tens of nL can be uniformly dispensed into the oil chamber without reduction in nozzle size. Based on the features of the proposed method (e.g., formation of droplets with controllable polarity and amount of electric charge in water and oil system), a simple and straightforward method is developed for microparticle synthesis, including preparation of colloidosomes and fabrication of Janus microparticles with anisotropic internal structures. Finally, a combined system consisting of ECC-induced droplet dispensing and electrophoresis of charged droplet (ECD)-driven manipulation systems is constructed. This integrated platform will provide increased utility and flexibility in microfluidic applications because a charged droplet can be delivered toward the intended position by programmable electric control. PMID:27534580

Direct observation of trapped charges under field-plate in p-GaN gate AlGaN/GaN high electron mobility transistors by electric field-induced optical second-harmonic generation

NASA Astrophysics Data System (ADS)

Katsuno, Takashi; Manaka, Takaaki; Soejima, Narumasa; Iwamoto, Mitsumasa

2017-02-01

Trapped charges underneath the field-plate (FP) in a p-gallium nitride (GaN) gate AlGaN/ GaN high electron mobility transistor device were visualized by using electric field-induced optical second-harmonic generation imaging. Second-harmonic (SH) signals in the off-state of the device with FP indicated that the electric field decreased at the p-GaN gate edge and concentrated at the FP edge. Nevertheless, SH signals originating from trapped charges were slightly observed at the p-GaN gate edge and were not observed at the FP edge in the on-state. Compared with the device without FP, reduction of trapped charges at the p-GaN gate edge of the device with FP is attributed to attenuation of the electric field with the aid of the FP. Negligible trapped charges at the FP edge is owing to lower trap density of the SiO2/AlGaN interface at the FP edge compared with that of the SiO2/p-GaN sidewall interface at the p-GaN gate edge and attenuated electric field by the thickness of the SiO2 passivation layer on the AlGaN surface.

Oxygen reduction on a Pt(111) catalyst in HT-PEM fuel cells by density functional theory

NASA Astrophysics Data System (ADS)

Sun, Hong; Li, Jie; Almheiri, Saif; Xiao, Jianyu

2017-08-01

The oxygen reduction reaction plays an important role in the performance of high-temperature proton exchange membrane (HT-PEM) fuel cells. In this study, a molecular dynamics model, which is based on the density functional theory and couples the system's energy, the exchange-correlation energy functional, the charge density distribution function, and the simplified Kohn-Sham equation, was developed to simulate the oxygen reduction reaction on a Pt(111) surface. Additionally, an electrochemical reaction system on the basis of a four-electron reaction mechanism was also developed for this simulation. The reaction path of the oxygen reduction reaction, the product structure of each reaction step and the system's energy were simulated. It is found that the first step reaction of the first hydrogen ion with the oxygen molecule is the controlling step of the overall reaction. Increasing the operating temperature speeds up the first step reaction rate and slightly decreases its reaction energy barrier. Our results provide insight into the working principles of HT-PEM fuel cells.

Direct measurement of sub-Debye-length attraction between oppositely charged surfaces.

PubMed

Kampf, Nir; Ben-Yaakov, Dan; Andelman, David; Safran, S A; Klein, Jacob

2009-09-11

Using a surface force balance with fast video analysis, we have measured directly the attractive forces between oppositely charged solid surfaces (charge densities sigma(+), sigma(-)) across water over the entire range of interaction, in particular, at surface separations D below the Debye screening length lambda(S). At very low salt concentration we find a long-ranged attraction between the surfaces (onset ca. 100 nm), whose variation at D

Influence of metallic surface states on electron affinity of epitaxial AlN films

NASA Astrophysics Data System (ADS)

Mishra, Monu; Krishna, Shibin; Aggarwal, Neha; Gupta, Govind

2017-06-01

The present article investigates surface metallic states induced alteration in the electron affinity of epitaxial AlN films. AlN films grown by plasma-assisted molecular beam epitaxy system with (30% and 16%) and without metallic aluminium on the surface were probed via photoemission spectroscopic measurements. An in-depth analysis exploring the influence of metallic aluminium and native oxide on the electronic structure of the films is performed. It was observed that the metallic states pinned the Fermi Level (FL) near valence band edge and lead to the reduction of electron affinity (EA). These metallic states initiated charge transfer and induced changes in surface and interface dipoles strength. Therefore, the EA of the films varied between 0.6-1.0 eV due to the variation in contribution of metallic states and native oxide. However, the surface barrier height (SBH) increased (4.2-3.5 eV) adversely due to the availability of donor-like surface states in metallic aluminium rich films.

High surface area LaMnO3 nanoparticles enhancing electrochemical catalytic activity for rechargeable lithium-air batteries

NASA Astrophysics Data System (ADS)

Li, Chuanhua; Yu, Zhiyong; Liu, Hanxing; Chen, Kang

2018-02-01

To improve sluggish kinetics of ORR and OER (oxygen reduction and evolution reaction) on the air electrode, the high surface area LaMnO3 nanoparticle catalysts were synthesized by sol-gel method. The specific surface area of as-synthesized pure phase LaMnO3 nanoparticles is 21.21 m2 g-1. The onset potential of high surface area LaMnO3 in alkaline solution is -0.0202 V which is comparable to commercial Pt/C. When the assembled high surface area LaMnO3-based lithium-air batteries were measured at 100 mA g-1, the initial discharge specific capacity could reach 6851.9 mA h g-1(carbon). In addition, lithium-oxygen batteries including high surface area LaMnO3 catalysts could be cycled for 52 cycles at 200 mA g-1 under a limited discharge-charge depth of 500 mA h gcarbon-1.

Electromagnetic studies of redox systems for energy storage

NASA Technical Reports Server (NTRS)

Wu, C. D.; Scherson, D.; Yeager, E.

1981-01-01

Both chromium and iron couples were studied on various electrode surfaces in acidic perchlorate solution by using rotating ring-disk techniques. It was found that chloride which forms inner sphere coordination complexes with the redox species enhances the electrode kinetics dramatically. The effects of lead underpotential deposition and surface alloy formation on the kinetics of the chromium couple on gold were studied using both linear sweep voltammetry and potential step techniques. The lad underpotential deposition was found to slow down the kinetics of the reduction of the Cr species on gold surfaces although increase the hydrogen overvoltage. The effect on the chromium kinetics can be explained in terms of principally a double layer effect. The underpotential deposition lead species with its positive charge results in a decrease in the concentration of the Cr species at the electrode surface. Similar phenomena were also observed with bismuth underpotential deposition on gold for the iron couple.

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy

PubMed Central

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-01-01

Local surface charge density of lipid membranes influences membrane–protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values. PMID:27561322

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy

NASA Astrophysics Data System (ADS)

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-08-01

Local surface charge density of lipid membranes influences membrane-protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values.

Mapping surface charge density of lipid bilayers by quantitative surface conductivity microscopy.

PubMed

Klausen, Lasse Hyldgaard; Fuhs, Thomas; Dong, Mingdong

2016-08-26

Local surface charge density of lipid membranes influences membrane-protein interactions leading to distinct functions in all living cells, and it is a vital parameter in understanding membrane-binding mechanisms, liposome design and drug delivery. Despite the significance, no method has so far been capable of mapping surface charge densities under physiologically relevant conditions. Here, we use a scanning nanopipette setup (scanning ion-conductance microscope) combined with a novel algorithm to investigate the surface conductivity near supported lipid bilayers, and we present a new approach, quantitative surface conductivity microscopy (QSCM), capable of mapping surface charge density with high-quantitative precision and nanoscale resolution. The method is validated through an extensive theoretical analysis of the ionic current at the nanopipette tip, and we demonstrate the capacity of QSCM by mapping the surface charge density of model cationic, anionic and zwitterionic lipids with results accurately matching theoretical values.

Surface charges for gravity and electromagnetism in the first order formalism

NASA Astrophysics Data System (ADS)

Frodden, Ernesto; Hidalgo, Diego

2018-02-01

A new derivation of surface charges for 3  +  1 gravity coupled to electromagnetism is obtained. Gravity theory is written in the tetrad-connection variables. The general derivation starts from the Lagrangian, and uses the covariant symplectic formalism in the language of forms. For gauge theories, surface charges disentangle physical from gauge symmetries through the use of Noether identities and the exactness symmetry condition. The surface charges are quasilocal, explicitly coordinate independent, gauge invariant and background independent. For a black hole family solution, the surface charge conservation implies the first law of black hole mechanics. As a check, we show the first law for an electrically charged, rotating black hole with an asymptotically constant curvature (the Kerr–Newman (anti-)de Sitter family). The charges, including the would-be mass term appearing in the first law, are quasilocal. No reference to the asymptotic structure of the spacetime nor the boundary conditions is required and therefore topological terms do not play a rôle. Finally, surface charge formulae for Lovelock gravity coupled to electromagnetism are exhibited, generalizing the one derived in a recent work by Barnich et al Proc. Workshop ‘ About Various Kinds of Interactions’ in honour of Philippe Spindel (4–5 June 2015, Mons, Belgium) C15-06-04 (2016 (arXiv:1611.01777 [gr-qc])). The two different symplectic methods to define surface charges are compared and shown equivalent.

Electrocatalytic activity of spots of electrodeposited noble-metal catalysts on carbon nanotubes modified glassy carbon.

PubMed

Chen, Xingxing; Eckhard, Kathrin; Zhou, Min; Bron, Michael; Schuhmann, Wolfgang

2009-09-15

A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.

Room temperature Zinc-metallation of cationic porphyrin at graphene surface and enhanced photoelectrocatalytic activity

NASA Astrophysics Data System (ADS)

Zeng, Rongjin; Chen, Guoliang; Xiong, Chungang; Li, Gengxian; Zheng, Yinzhi; Chen, Jian; Long, Yunfei; Chen, Shu

2018-03-01

A stable zincporphyrin functionalized graphene nanocomposite was prepared by using positively charged cationic porphyrin (5,10,15,20-tetra(4-propyl pyridinio) porphyrin, TPPyP) and successive reduced graphene oxide (rGO) with tuned negative charge. The nanocomposite preparation was accompanied first by distinct electrostatic interactions and π-π stacking between TPPyP and rGO, and followed by fast Zinc-metallation at room temperature. In contrast to free TPPyP with Zn2+, the incorporation reaction is very slow at room temperature and heating or reflux conditions are required to increase the metallation rate. While at the surface of rGO nanosheet, the Zinc-metallation of TPPyP was greatly accelerated to 30 min at 25 °C in aqueous solution. The interaction process and composites formation were fully revealed by significant variations in UV-vis absorption spectra, X-ray photoelectron spectra (XPS) measurements, atomic force microscope (AFM) images, and fluorescence spectra. Furthermore, photoelectrochemical activity of resultant rGO/TPPyP-Zn nanocomposites was evaluated under visible-light irradiation, and enhancement of the photoelectrocatalytic reduction of CO2 was achieved.

Axial iron coordination and spin state change in a heme c upon electrostatic protein-SAM interaction.

PubMed

Di Rocco, Giulia; Ranieri, Antonio; Bortolotti, Carlo Augusto; Battistuzzi, Gianantonio; Bonifacio, Alois; Sergo, Valter; Borsari, Marco; Sola, Marco

2013-08-28

A bacterial di-heme cytochrome c binds electrostatically to a gold electrode surface coated with a negatively charged COOH-terminated SAM adopting a sort of 'perpendicular' orientation. Cyclic voltammetry, Resonance Raman and SERRS spectroscopies indicate that the high-potential C-terminal heme center proximal to the SAM's surface undergoes an adsorption-induced swapping of one axial His ligand with a water molecule, which is probably lost in the reduced form, and a low- to high-spin transition. This coordination change for a bis-His ligated heme center upon an electrostatically-driven molecular recognition is as yet unprecedented, as well as the resulting increase in reduction potential. We discuss it in comparison with the known methionine ligand lability in monoheme cytochromes c occurring upon interaction with charged molecular patches. One possible implication of this finding in biological ET is that mobile redox partners do not behave as rigid and invariant bodies, but in the ET complex are subjected to molecular changes and structural fluctuations that affect in a complex way the thermodynamics and the kinetics of the process.

Correlation of film morphology and defect content with the charge-carrier transport in thin-film transistors based on ZnO nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polster, S.; Jank, M. P. M.; Frey, L.

2016-01-14

The correlation of defect content and film morphology with the charge-carrier transport in field-effect devices based on zinc oxide nanoparticles was investigated. Changes in the defect content and the morphology were realized by annealing and sintering of the nanoparticle thin films. Temperature-dependent electrical measurements reveal that the carrier transport is thermally activated for both the unsintered and sintered thin films. Reduced energetic barrier heights between the particles have been determined after sintering. Additionally, the energetic barrier heights between the particles can be reduced by increasing the drain-to-source voltage and the gate-to-source voltage. The changes in the barrier height are discussedmore » with respect to information obtained by scanning electron microscopy and photoluminescence measurements. It is found that a reduction of surface states and a lower roughness at the interface between the particle layer and the gate dielectric lead to lower barrier heights. Both surface termination and layer morphology at the interface affect the barrier height and thus are the main criteria for mobility improvement and device optimization.« less

Direct Observation of Charge Transfer at a MgO(111) Surface

NASA Astrophysics Data System (ADS)

Subramanian, A.; Marks, L. D.; Warschkow, O.; Ellis, D. E.

2004-01-01

Transmission electron diffraction (TED) combined with direct methods have been used to study the √(3)×√(3)R30° reconstruction on the polar (111) surface of MgO and refine the valence charge distribution. The surface is nonstoichiometric and is terminated by a single magnesium atom. A charge-compensating electron hole is localized in the next oxygen layer and there is a nominal charge transfer from the oxygen atoms to the top magnesium atom. The partial charges that we obtain for the surface atoms are in reasonable agreement with empirical bond-valence estimations.

The surface charge of trypanosomatids.

PubMed

Souto-Padrón, Thaïs

2002-12-01

The surface charge of trypanosomatids was evaluated by means of the binding of cationic particles, as visualized by electron microscopy and by direct measurements of the electrophoretic mobility of cells. The results obtained indicate that most of the trypanosomatids exhibit a negatively charged surface whose value is species specific and varies according to the developmental stages. Sialic acids associated with glycoproteins, glycolipids and phosphate groups are the major components responsible for the net negative surface charge of the trypanosomatids.

Miniaturized ultrafine particle sizer and monitor

NASA Technical Reports Server (NTRS)

Qi, Chaolong (Inventor); Chen, Da-Ren (Inventor)

2011-01-01

An apparatus for measuring particle size distribution includes a charging device and a precipitator. The charging device includes a corona that generates charged ions in response to a first applied voltage, and a charger body that generates a low energy electrical field in response to a second applied voltage in order to channel the charged ions out of the charging device. The corona tip and the charger body are arranged relative to each other to direct a flow of particles through the low energy electrical field in a direction parallel to a direction in which the charged ions are channeled out of the charging device. The precipitator receives the plurality of particles from the charging device, and includes a disk having a top surface and an opposite bottom surface, wherein a predetermined voltage is applied to the top surface and the bottom surface to precipitate the plurality of particles.

Method of adhesion between an oxide layer and a metal layer

DOEpatents

Jennison, Dwight R.; Bogicevic, Alexander; Kelber, Jeffry A.; Chambers, Scott A.

2004-09-14

A method of controlling the wetting characteristics and increasing the adhesion between a metal and an oxide layer. By introducing a negatively-charged species to the surface of an oxide layer, layer-by-layer growth of metal deposited onto the oxide surface is promoted, increasing the adhesion strength of the metal-oxide interface. The negatively-charged species can either be deposited onto the oxide surface or a compound can be deposited that dissociates on, or reacts with, the surface to form the negatively-charged species. The deposited metal adatoms can thereby bond laterally to the negatively-charged species as well as vertically to the oxide surface as well as react with the negatively charged species, be oxidized, and incorporated on or into the surface of the oxide.

The capacitive proximity sensor based on transients in RC-circuits

NASA Astrophysics Data System (ADS)

Yakunin, A. G.

2018-05-01

The principle of operation of the capacitive proximity sensor is described. It can be used in various robotic complexes, automation systems and alarm devices to inform the control device of the approach to the sensor sensitive surface of an object. At the heart of the device is the measurement of the change in the current of the transient accompanying the charge of the reference capacitor because of the parallel connection to it the capacitance formed by the sensitive sensor surface and the external object. At the heart of the device is the measurement of the change in the current of the transient accompanying the charge of the reference capacitor caused by the parallel connection to it the capacitance formed by the sensitive sensor surface and the external object. As shown by theoretical and experimental studies, the value of this capacity, depending on the purpose of the device, can vary within very wide limits. In this case, the sensitive surface can be both a piece of ordinary wire several centimeters long, and a metall plate or grid, the area of which can reach units and even tens of square meters. The main advantage of the proposed solution is a significant reduction in the effect of spurious leakage currents arising at the capacitance of the measuring electrode under the influence of pollution and humidity of the environment.

Determination of gas phase protein ion densities via ion mobility analysis with charge reduction.

PubMed

Maisser, Anne; Premnath, Vinay; Ghosh, Abhimanyu; Nguyen, Tuan Anh; Attoui, Michel; Hogan, Christopher J

2011-12-28

We use a charge reduction electrospray (ESI) source and subsequent ion mobility analysis with a differential mobility analyzer (DMA, with detection via both a Faraday cage electrometer and a condensation particle counter) to infer the densities of single and multiprotein ions of cytochrome C, lysozyme, myoglobin, ovalbumin, and bovine serum albumin produced from non-denaturing (20 mM aqueous ammonium acetate) and denaturing (1 : 49.5 : 49.5, formic acid : methanol : water) ESI. Charge reduction is achieved through use of a Po-210 radioactive source, which generates roughly equal concentrations of positive and negative ions. Ions produced by the source collide with and reduce the charge on ESI generated drops, preventing Coulombic fissions, and unlike typical protein ESI, leading to gas-phase protein ions with +1 to +3 excess charges. Therefore, charge reduction serves to effectively mitigate any role that Coulombic stretching may play on the structure of the gas phase ions. Density inference is made via determination of the mobility diameter, and correspondingly the spherical equivalent protein volume. Through this approach it is found that for both non-denaturing and denaturing ESI-generated ions, gas-phase protein ions are relatively compact, with average densities of 0.97 g cm(-3) and 0.86 g cm(-3), respectively. Ions from non-denaturing ESI are found to be slightly more compact than predicted from the protein crystal structures, suggesting that low charge state protein ions in the gas phase are slightly denser than their solution conformations. While a slight difference is detected between the ions produced with non-denaturing and denaturing ESI, the denatured ions are found to be much more dense than those examined previously by drift tube mobility analysis, in which charge reduction was not employed. This indicates that Coulombic stretching is typically what leads to non-compact ions in the gas-phase, and suggests that for gas phase measurements to be correlated to biomolecular structures in solution, low charge state ions should be analyzed. Further, to determine if different solution conditions give rise to ions of different structure, ions of similar charge state should be compared. Non-denatured protein ion densities are found to be in excellent agreement with non-denatured protein ion densities inferred from prior DMA and drift tube measurements made without charge reduction (all ions with densities in the 0.85-1.10 g cm(-3) range), showing that these ions are not strongly influenced by Coulombic stretching nor by analysis method.

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode.

PubMed

Wang, Liying; Gupta, Kalyani; Goodall, Josephine B M; Darr, Jawwad A; Holt, Katherine B

2017-04-28

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO 3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(i) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO 2 saturated KHCO 3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO 2 . On cycling to negative potentials, larger reduction currents were observed in the presence of CO 2 ; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO 2 CuO underwent reduction to Cu 2 O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO 2 Reduction

DOE PAGES

Medina Ramos, Jonnathan; Zhang, Weiwei; Yoon, Kichul; ...

2018-03-08

Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im])(+))-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi 2O 3 layer. This oxide layer gets reduced to Bi(0)during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM](+)) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCI due to a similar to 4-10% thinning and a similar to 40% decrease in lateral sizemore » of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im] + cations bind to the metal surface more strongly than tetrabutylammonium (TBA +) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im](+)cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi center dot center dot center dot[Im] + complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi center dot center dot center dot[Im] + complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO 2 .« less

Cathodic Corrosion at the Bismuth-Ionic Liquid Electrolyte Interface under Conditions for CO 2 Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Medina Ramos, Jonnathan; Zhang, Weiwei; Yoon, Kichul

Bismuth electrodes undergo distinctive electrochemically induced structural changes in nonaqueous imidazolium ([Im])(+))-based ionic liquid solutions under cathodic polarization. In situ X-ray reflectivity (XR) studies have been undertaken to probe well-ordered Bi (001) films which originally contain a native Bi 2O 3 layer. This oxide layer gets reduced to Bi(0)during the first cyclic voltammetry (CV) scan in acetonitrile solutions containing 1-butyl-3-methylimidazolium ([BMIM](+)) electrolytes. Approximately 60% of the Bi (001) Bragg peak reflectivity is lost during a potential sweep between -1.5 and -1.9 V vs Ag/AgCI due to a similar to 4-10% thinning and a similar to 40% decrease in lateral sizemore » of Bi (001) domains, which are mostly reversed during the anodic scan. Repeated potential cycling enhances the thinning and roughening of the films, suggesting that partial dissolution of Bi ensues during negative polarization. The mechanism of this behavior is understood through molecular dynamics simulations using ReaxFF and density functional theory (DFT) calculations. Both approaches indicate that [Im] + cations bind to the metal surface more strongly than tetrabutylammonium (TBA +) as the potential and the charge on the Bi surface become more negative. ReaxFF simulations predict a higher degree of disorder for a negatively charged Bi (001) slab in the presence of the [Im](+)cations and substantial migration of Bi atoms from the surface. DFT simulations show the formation of Bi center dot center dot center dot[Im] + complexes that lead to the dissolution of Bi atoms from step edges on the Bi (001) surface at potentials between -1.65 and -1.95 V. Bi desorption from a flat terrace requires a potential of approximately -2.25 V. Together, these results suggest the formation of a Bi center dot center dot center dot[Im] + complex through partial cathodic corrosion of the Bi film under conditions (potential and electrolyte composition) that favor the catalytic reduction of CO 2 .« less

Method and system for treating an interior surface of a workpiece using a charged particle beam

DOEpatents

Swenson, David Richard

2007-05-23

A method and system of treating an interior surface on an internal cavity of a workpiece using a charged particle beam. A beam deflector surface of a beam deflector is placed within the internal cavity of the workpiece and is used to redirect the charged particle beam toward the interior surface to treat the interior surface.

Determination of molecular configuration by debye length modulation.

PubMed

Vacic, Aleksandar; Criscione, Jason M; Rajan, Nitin K; Stern, Eric; Fahmy, Tarek M; Reed, Mark A

2011-09-07

Silicon nanowire field effect transistors (FETs) have emerged as ultrasensitive, label-free biodetectors that operate by sensing bound surface charge. However, the ionic strength of the environment (i.e., the Debye length of the solution) dictates the effective magnitude of the surface charge. Here, we show that control of the Debye length determines the spatial extent of sensed bound surface charge on the sensor. We apply this technique to different methods of antibody immobilization, demonstrating different effective distances of induced charge from the sensor surface.

Mapping the surface charge distribution of amyloid fibril

NASA Astrophysics Data System (ADS)

Lee, Gyudo; Lee, Wonseok; Lee, Hyungbeen; Woo Lee, Sang; Sung Yoon, Dae; Eom, Kilho; Kwon, Taeyun

2012-07-01

It is of high importance to measure and map the surface charge distribution of amyloids, since electrostatic interaction between amyloidogenic proteins and biomolecules plays a vital role in amyloidogenesis. In this work, we have measured and mapped the surface charge distributions of amyloids (i.e., β-lactoglobulin fibril) using Kelvin probe force microscopy. It is shown that the surface charge distribution is highly dependent on the conformation of amyloids (e.g., the helical pitch of amyloid fibrils) as well as the pH of a solvent.

Charging Characteristics of an Insulating Hollow Cylinder in Vacuum

NASA Astrophysics Data System (ADS)

Yamamoto, Osamu; Hayashi, Hirotaka; Wadahama, Toshihiko; Takeda, Daisuke; Hamada, Shoji; Ohsawa, Yasuharu

This paper deals with charging characteristics of the inner surface of an insulating hollow cylinder in vacuum. We conducted measurements of electric field strength near the triple points on cathode by using an electrostatic probe. Also we conducted a computer simulation of charging based on the Secondary Electron Emission Avalanche (SEEA) mechanism. These results are compared with those obtained previously for solid cylinders. As a result, we have clarified that hollow cylinders acquire surface charge which is larger than that of solid cylinders. We have also found that charge controlling effect by roughening the inner surface, which have been proved effective to depress charging on the surface of solid cylinders in our previous studies, is limited for hollow cylinders.

Relating Silica Scaling in Reverse Osmosis to Membrane Surface Properties.

PubMed

Tong, Tiezheng; Zhao, Song; Boo, Chanhee; Hashmi, Sara M; Elimelech, Menachem

2017-04-18

We investigated the relationship between membrane surface properties and silica scaling in reverse osmosis (RO). The effects of membrane hydrophilicity, free energy for heterogeneous nucleation, and surface charge on silica scaling were examined by comparing thin-film composite polyamide membranes grafted with a variety of polymers. Results show that the rate of silica scaling was independent of both membrane hydrophilicity and free energy for heterogeneous nucleation. In contrast, membrane surface charge demonstrated a strong correlation with the extent of silica scaling (R 2 > 0.95, p < 0.001). Positively charged membranes significantly facilitated silica scaling, whereas a more negative membrane surface charge led to reduced scaling. This observation suggests that deposition of negatively charged silica species on the membrane surface plays a critical role in silica scale formation. Our findings provide fundamental insights into the mechanisms governing silica scaling in reverse osmosis and highlight the potential of membrane surface modification as a strategy to reduce silica scaling.

Molecular dynamics investigation of the ionic liquid/enzyme interface: application to engineering enzyme surface charge.

PubMed

Burney, Patrick R; Nordwald, Erik M; Hickman, Katie; Kaar, Joel L; Pfaendtner, Jim

2015-04-01

Molecular simulations of the enzymes Candida rugosa lipase and Bos taurus α-chymotrypsin in aqueous ionic liquids 1-butyl-3-methylimidazolium chloride and 1-ethyl-3-methylimidazolium ethyl sulfate were used to study the change in enzyme-solvent interactions induced by modification of the enzyme surface charge. The enzymes were altered by randomly mutating lysine surface residues to glutamate, effectively decreasing the net surface charge by two for each mutation. These mutations resemble succinylation of the enzyme by chemical modification, which has been shown to enhance the stability of both enzymes in ILs. After establishing that the enzymes were stable on the simulated time scales, we focused the analysis on the organization of the ionic liquid substituents about the enzyme surface. Calculated solvent charge densities show that for both enzymes and in both solvents that changing positively charged residues to negative charge does indeed increase the charge density of the solvent near the enzyme surface. The radial distribution of IL constituents with respect to the enzyme reveals decreased interactions with the anion are prevalent in the modified systems when compared to the wild type, which is largely accompanied by an increase in cation contact. Additionally, the radial dependence of the charge density and ion distribution indicates that the effect of altering enzyme charge is confined to short range (≤1 nm) ordering of the IL. Ultimately, these results, which are consistent with that from prior experiments, provide molecular insight into the effect of enzyme surface charge on enzyme stability in ILs. © 2015 Wiley Periodicals, Inc.

Competitive Adsorption and Ordered Packing of Counterions near Highly Charged Surfaces: From Mean-Field Theory to Monte Carlo Simulations

PubMed Central

Wen, Jiayi; Zhou, Shenggao; Xu, Zhenli; Li, Bo

2013-01-01

Competitive adsorption of counterions of multiple species to charged surfaces is studied by a size-effect included mean-field theory and Monte Carlo (MC) simulations. The mean-field electrostatic free-energy functional of ionic concentrations, constrained by Poisson’s equation, is numerically minimized by an augmented Lagrangian multiplier method. Unrestricted primitive models and canonical ensemble MC simulations with the Metropolis criterion are used to predict the ionic distributions around a charged surface. It is found that, for a low surface charge density, the adsorption of ions with a higher valence is preferable, agreeing with existing studies. For a highly charged surface, both of the mean-field theory and MC simulations demonstrate that the counterions bind tightly around the charged surface, resulting in a stratification of counterions of different species. The competition between mixed entropy and electrostatic energetics leads to a compromise that the ionic species with a higher valence-to-volume ratio has a larger probability to form the first layer of stratification. In particular, the MC simulations confirm the crucial role of ionic valence-to-volume ratios in the competitive adsorption to charged surfaces that had been previously predicted by the mean-field theory. The charge inversion for ionic systems with salt is predicted by the MC simulations but not by the mean-field theory. This work provides a better understanding of competitive adsorption of counterions to charged surfaces and calls for further studies on the ionic size effect with application to large-scale biomolecular modeling. PMID:22680474

Competitive adsorption and ordered packing of counterions near highly charged surfaces: From mean-field theory to Monte Carlo simulations.

PubMed

Wen, Jiayi; Zhou, Shenggao; Xu, Zhenli; Li, Bo

2012-04-01

Competitive adsorption of counterions of multiple species to charged surfaces is studied by a size-effect-included mean-field theory and Monte Carlo (MC) simulations. The mean-field electrostatic free-energy functional of ionic concentrations, constrained by Poisson's equation, is numerically minimized by an augmented Lagrangian multiplier method. Unrestricted primitive models and canonical ensemble MC simulations with the Metropolis criterion are used to predict the ionic distributions around a charged surface. It is found that, for a low surface charge density, the adsorption of ions with a higher valence is preferable, agreeing with existing studies. For a highly charged surface, both the mean-field theory and the MC simulations demonstrate that the counterions bind tightly around the charged surface, resulting in a stratification of counterions of different species. The competition between mixed entropy and electrostatic energetics leads to a compromise that the ionic species with a higher valence-to-volume ratio has a larger probability to form the first layer of stratification. In particular, the MC simulations confirm the crucial role of ionic valence-to-volume ratios in the competitive adsorption to charged surfaces that had been previously predicted by the mean-field theory. The charge inversion for ionic systems with salt is predicted by the MC simulations but not by the mean-field theory. This work provides a better understanding of competitive adsorption of counterions to charged surfaces and calls for further studies on the ionic size effect with application to large-scale biomolecular modeling.

Battery Power Management in Heavy-duty HEVs based on the Estimated Critical Surface Charge

DTIC Science & Technology

2011-03-01

health prospects without any penalty on fuel efficiency. Keywords: Lithium - ion battery ; power management; critical surface charge; Lithium-ion...fuel efficiency. 15. SUBJECT TERMS Lithium - ion battery ; power management; critical surface charge; Lithium-ion concentration; estimation; extended...Di Domenico, D., Fiengo, G., and Stefanopoulou, A. (2008) ’ Lithium - ion battery state of charge estimation with a kalman filter based on a

Size, surface, and compositional tuning of the electronic and photocatalytic properties of II-VI quantum-size semiconductor nanocrystals

NASA Astrophysics Data System (ADS)

Korgel, Brian Allan

1997-11-01

Phosphatidylcholine vesicles provide reaction compartments for synthesis of size-quantized CdS nanocrystals of dimension predicted to within ±2 A based on initial encapsulated CdClsb2 concentration and vesicle diameter. Vesicle formation by detergent dialysis of phosphatidylcholine/hexylglucoside mixed micelles yields highly monodisperse lipid capsules within which monodisperse CdS nanoparticles are precipitated with sulfide. Size-quantized CdS nanocrystals, with diameters ranging from 20 to 60 A, have been produced with typical standard deviations about the mean diameter of ±8% as measured by transmission electron microscopy. By including ZnClsb2 or HgClsb2 in the dialyzate prior to vesicle formation, quantum-sized Znsb{y}Cdsb{1-y}S or Hgsb{y}Cdsb{1-y}S nanocrystal alloys with controlled stoichiometry are generated. Spectrophotometric and spectrofluorimetric measurements are consistent with highly crystalline, monodisperse particles with few core or surface defects. The alloyed nanocrystal spectra shift consistently with composition indicating a high degree of compositional control. Measured exciton energies for CdS show excellent agreement with data in the literature. The empirical pseudopotential model presented by Ramakrishna and Friesner for a cubic CdS lattice, correcting for experimentally measured lattice contractions, best fits the data. Size-quantized CdS nanocrystals serve as photocatalysts for nitrate reduction at neutral pH under conditions that mimic illumination by sunlight with overall product quantum yields of up to 4% for {˜}20 A, amine-terminated particles. Due to the effects of quantum confinement on electron and hole redox potentials, photocatalyzed nitrate reduction rates depend strongly on the particle size, and the fastest reduction rates are observed with the smallest nanocrystals. Using a Tafel plot and the empirical pseudopotential model to estimate electron redox potentials, the apparent electron transfer coefficient and the apparent standard rate constant is estimated at 0.23 and 4.0× 10sp{-12} cm/sec, respectively, for amine-terminated particles. Nitrate adsorption is important in this system and the effect on photoreduction rates is described well by a Langmuir-Hinschelwood expression. Nitrate reduction rates are reduced two-fold or more on negatively charged, carboxy-terminated nanocrystals that electrostatically repel nitrate. Reaction rates are additionally influenced by competetive chloride adsorption and surface charge modification due to solution pH.

Aggregation and charging of sulfate and amidine latex particles in the presence of oxyanions.

PubMed

Sugimoto, Takuya; Cao, Tianchi; Szilagyi, Istvan; Borkovec, Michal; Trefalt, Gregor

2018-08-15

Electrophoretic mobility and time resolved light scattering are used to measure the effect on charging and aggregation of amidine and sulfate latex particles of different oxyanions namely, phosphate, arsenate, sulfate, and selenate. In the case of negatively charged sulfate latex particles oxyanions represent the coions, while they represent counterions in the case of the positively charged amidine latex. Repulsive interaction between the sulfate latex surface and the coions results in weak ion specific effects on the charging and aggregation. On the other hand the interaction of oxyanions with the amidine latex surface is highly specific. The monovalent dihydrogen phosphate ion strongly adsorbs to the positively charged surface and reverses the charge of the particle. This charge reversal leads also to the restabilization of the amidine latex suspension at the intermediate phosphate concentrations. In the case of dihydrogen arsenate the adsorption to amidine latex surface is weaker and no charge reversal and restabilization occurs. Similar differences are seen between the sulfate and selenate analogues, where selenate adsorbs more strongly to the surface as compared to the sulfate ion and invokes charge reversal. The present results indicate that ion specificity is much more pronounced in the case of counterions. Copyright © 2018 Elsevier Inc. All rights reserved.

Spontaneous Droplet Jump with Electro-Bouncing

NASA Astrophysics Data System (ADS)

Schmidt, Erin; Weislogel, Mark

2016-11-01

We investigate the dynamics of water droplet jumps from superhydrophobic surfaces in the presence of an electric field during a step reduction in gravity level. In the brief free-fall environment of a drop tower, when a strong non-homogeneous electric field (with a measured strength between 0 . 39 and 2 . 36 kV/cm) is imposed, body forces acting on the jumped droplets are primarily supplied by polarization stress and Coulombic attraction instead of gravity. The droplet charge, measured to be on the order of 2 . 3 . (10-11) C, originates by electro-osmosis of charged species at the (PTFE coated) hydrophobic surface interface. This electric body force leads to a droplet bouncing behavior similar to well-known phenomena in 1-g, though occurring for larger drops 0.1 mL for a given range of impact Weber numbers, We < 20 . In 1-g, for We > 0 . 4 , impact recoil behavior on a super-hydrophobic surface is normally dominated by damping from contact line hysteresis and by air-layer interactions. However, in the strong electric field, the droplet bounce dynamics additionally include electrohydrodynamic effects on wettability and Cassie-Wenzel transition. This is qualitatively discussed in terms of coefficients of restitution and trends in contact time. This work was supported primarily by NASA Cooperative Agreement NNX12A047A.

Reduction of thermal conductivity in phononic nanomesh structures.

PubMed

Yu, Jen-Kan; Mitrovic, Slobodan; Tham, Douglas; Varghese, Joseph; Heath, James R

2010-10-01

Controlling the thermal conductivity of a material independently of its electrical conductivity continues to be a goal for researchers working on thermoelectric materials for use in energy applications and in the cooling of integrated circuits. In principle, the thermal conductivity κ and the electrical conductivity σ may be independently optimized in semiconducting nanostructures because different length scales are associated with phonons (which carry heat) and electric charges (which carry current). Phonons are scattered at surfaces and interfaces, so κ generally decreases as the surface-to-volume ratio increases. In contrast, σ is less sensitive to a decrease in nanostructure size, although at sufficiently small sizes it will degrade through the scattering of charge carriers at interfaces. Here, we demonstrate an approach to independently controlling κ based on altering the phonon band structure of a semiconductor thin film through the formation of a phononic nanomesh film. These films are patterned with periodic spacings that are comparable to, or shorter than, the phonon mean free path. The nanomesh structure exhibits a substantially lower thermal conductivity than an equivalently prepared array of silicon nanowires, even though this array has a significantly higher surface-to-volume ratio. Bulk-like electrical conductivity is preserved. We suggest that this development is a step towards a coherent mechanism for lowering thermal conductivity.

Role of protein surface charge in monellin sweetness.

PubMed

Xue, Wei-Feng; Szczepankiewicz, Olga; Thulin, Eva; Linse, Sara; Carey, Jannette

2009-03-01

A small number of proteins have the unusual property of tasting intensely sweet. Despite many studies aimed at identifying their sweet taste determinants, the molecular basis of protein sweetness is not fully understood. Recent mutational studies of monellin have implicated positively charged residues in sweetness. In the present work, the effect of overall net charge was investigated using the complementary approach of negative charge alterations. Multiple substitutions of Asp/Asn and Glu/Gln residues radically altered the surface charge of single-chain monellin by removing six negative charges or adding four negative charges. Biophysical characterization using circular dichroism, fluorescence, and two-dimensional NMR demonstrates that the native fold of monellin is preserved in the variant proteins under physiological solution conditions although their stability toward chemical denaturation is altered. A human taste test was employed to determine the sweetness detection threshold of the variants. Removal of negative charges preserves monellin sweetness, whereas added negative charge has a large negative impact on sweetness. Meta-analysis of published charge variants of monellin and other sweet proteins reveals a general trend toward increasing sweetness with increasing positive net charge. Structural mapping of monellin variants identifies a hydrophobic surface predicted to face the receptor where introduced positive or negative charge reduces sweetness, and a polar surface where charges modulate long-range electrostatic complementarity.

Fibronectin module FN(III)9 adsorption at contrasting solid model surfaces studied by atomistic molecular dynamics.

PubMed

Kubiak-Ossowska, Karina; Mulheran, Paul A; Nowak, Wieslaw

2014-08-21

The mechanism of human fibronectin adhesion synergy region (known as integrin binding region) in repeat 9 (FN(III)9) domain adsorption at pH 7 onto various and contrasting model surfaces has been studied using atomistic molecular dynamics simulations. We use an ionic model to mimic mica surface charge density but without a long-range electric field above the surface, a silica model with a long-range electric field similar to that found experimentally, and an Au {111} model with no partial charges or electric field. A detailed description of the adsorption processes and the contrasts between the various model surfaces is provided. In the case of our model silica surface with a long-range electrostatic field, the adsorption is rapid and primarily driven by electrostatics. Because it is negatively charged (-1e), FN(III)9 readily adsorbs to a positively charged surface. However, due to its partial charge distribution, FN(III)9 can also adsorb to the negatively charged mica model because of the absence of a long-range repulsive electric field. The protein dipole moment dictates its contrasting orientation at these surfaces, and the anchoring residues have opposite charges to the surface. Adsorption on the model Au {111} surface is possible, but less specific, and various protein regions might be involved in the interactions with the surface. Despite strongly influencing the protein mobility, adsorption at these model surfaces does not require wholesale FN(III)9 conformational changes, which suggests that the biological activity of the adsorbed protein might be preserved.

Charge heterogeneity of surfaces: mapping and effects on surface forces.

PubMed

Drelich, Jaroslaw; Wang, Yu U

2011-07-11

The DLVO theory treats the total interaction force between two surfaces in a liquid medium as an arithmetic sum of two components: Lifshitz-van der Waals and electric double layer forces. Despite the success of the DLVO model developed for homogeneous surfaces, a vast majority of surfaces of particles and materials in technological systems are of a heterogeneous nature with a mosaic structure composed of microscopic and sub-microscopic domains of different surface characteristics. In such systems, the heterogeneity of the surface can be more important than the average surface character. Attractions can be stronger, by orders of magnitude, than would be expected from the classical mean-field DLVO model when area-averaged surface charge or potential is employed. Heterogeneity also introduces anisotropy of interactions into colloidal systems, vastly ignored in the past. To detect surface heterogeneities, analytical tools which provide accurate and spatially resolved information about material surface chemistry and potential - particularly at microscopic and sub-microscopic resolutions - are needed. Atomic force microscopy (AFM) offers the opportunity to locally probe not only changes in material surface characteristic but also charges of heterogeneous surfaces through measurements of force-distance curves in electrolyte solutions. Both diffuse-layer charge densities and potentials can be calculated by fitting the experimental data with a DLVO theoretical model. The surface charge characteristics of the heterogeneous substrate as recorded by AFM allow the charge variation to be mapped. Based on the obtained information, computer modeling and simulation can be performed to study the interactions among an ensemble of heterogeneous particles and their collective motions. In this paper, the diffuse-layer charge mapping by the AFM technique is briefly reviewed, and a new Diffuse Interface Field Approach to colloid modeling and simulation is briefly discussed. Copyright © 2011 Elsevier B.V. All rights reserved.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1993-01-01

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1993-12-07

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1990-01-01

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, S.F.; Rauh, R.D.

1990-07-03

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counter electrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films. 4 figs.

Chemistry of fast electrons

PubMed Central

Maximoff, Sergey N.; Head-Gordon, Martin P.

2009-01-01

A chemicurrent is a flux of fast (kinetic energy ≳ 0.5−1.3 eV) metal electrons caused by moderately exothermic (1−3 eV) chemical reactions over high work function (4−6 eV) metal surfaces. In this report, the relation between chemicurrent and surface chemistry is elucidated with a combination of top-down phenomenology and bottom-up atomic-scale modeling. Examination of catalytic CO oxidation, an example which exhibits a chemicurrent, reveals 3 constituents of this relation: The localization of some conduction electrons to the surface via a reduction reaction, 0.5 O2 + δe− → Oδ− (Red); the delocalization of some surface electrons into a conduction band in an oxidation reaction, Oδ− + CO → CO2δ− → CO2 + δe− (Ox); and relaxation without charge transfer (Rel). Juxtaposition of Red, Ox, and Rel produces a daunting variety of metal electronic excitations, but only those that originate from CO2 reactive desorption are long-range and fast enough to dominate the chemicurrent. The chemicurrent yield depends on the universality class of the desorption process and the distribution of the desorption thresholds. This analysis implies a power-law relation with exponent 2.66 between the chemicurrent and the heat of adsorption, which is consistent with experimental findings for a range of systems. This picture also applies to other oxidation-reduction reactions over high work function metal surfaces. PMID:19561296

Kinetic Investigations of SiMn Slags From Different Mn Sources

NASA Astrophysics Data System (ADS)

Kim, Pyunghwa Peace; Tangstad, Merete

2018-06-01

The kinetics of MnO and SiO2 reduction were investigated for Silicomanganese (SiMn) slags using a Thermogravimetric analysis (TGA) between 1773 K and 1923 K (1500 °C and 1650 °C) under CO atmospheric pressure. The charge materials were based on Assmang ore and HC FeMn Slag. Rate models for MnO and SiO2 reduction were applied to describe the metal-producing rates, as shown by the following equations: r_{MnO} = k_{MnO} × A × ( {a_{MnO} - {a_{Mn} }/{K_{T }}} ) r_{{{SiO}2 }} = k_{SiO2} × A × ( {a_{{{SiO}2 }} - {a_{Si} }/{K_{T }}} ). The results show that the choice of raw materials in the charge considerably affected the reduction rate of MnO and SiO2. The highest reduction rate was found to be from charges using HC FeMn slag. The difference in the driving forces was insignificant among the SiMn slags, and the similar slag viscosities could not explain the different reduction rates. Instead, the difference is attributed to small amounts of sulfur and the amount of iron in the charge. In addition, the rate models were applicable to describe the reduction of MnO and SiO2 in SiMn slags.

Theoretical characterization on the size-dependent electron and hole trapping activity of chloride-passivated CdSe nanoclusters

NASA Astrophysics Data System (ADS)

Cui, Yingqi; Cui, Xianhui; Zhang, Li; Xie, Yujuan; Yang, Mingli

2018-04-01

Ligand passivation is often used to suppress the surface trap states of semiconductor quantum dots (QDs) for their continuous photoluminescence output. The suppression process is related to the electrophilic/nucleophilic activity of surface atoms that varies with the structure and size of QD and the electron donating/accepting nature of ligand. Based on first-principles-based descriptors and cluster models, the electrophilic/nucleophilic activities of bare and chloride-coated CdSe clusters were studied to reveal the suppression mechanism of Cl-passivated QDs and compared to experimental observations. The surface atoms of bare clusters have higher activity than inner atoms and their activity decreases with cluster size. In the ligand-coated clusters, the Cd atom remains as the electrophilic site, while the nucleophilic site of Se atoms is replaced by Cl atoms. The activities of Cd and Cl atoms in the coated clusters are, however, remarkably weaker than those in bare clusters. Cluster size, dangling atoms, ligand coverage, electronegativity of ligand atoms, and solvent (water) were found to have considerable influence on the activity of surface atoms. The suppression of surface trap states in Cl-passivated QDs was attributed to the reduction of electrophilic/nucleophilic activity of Cd/Se/Cl atoms. Both saturation to under-coordinated surface atoms and proper selection for the electron donating/accepting strength of ligands are crucial for eliminating the charge carrier traps. Our calculations predicted a similar suppressing effect of chloride ligands with experiments and provided a simple but effective approach to assess the charge carrier trapping behaviors of semiconductor QDs.

Potential health economic benefits of vitamin supplementation.

PubMed Central

Bendich, A; Mallick, R; Leader, S

1997-01-01

This study used published relative risk estimates for birth defects, premature birth, and coronary heart disease associated with vitamin intake to project potential annual cost reductions in U.S. hospitalization charges. Epidemiological and intervention studies with relative risk estimates were identified via MEDLINE. Preventable fraction estimates were derived from data on the percentage of at-risk Americans with daily vitamin intake levels lower than those associated with disease risk reduction. Hospitalization rates were obtained from the 1992 National Hospital Discharge Survey. Charge data from the 1993 California Hospital Discharge Survey were adjusted to 1995 national charges using the medical component of the Consumer Price Index. Based on published risk reductions, annual hospital charges for birth defects, low-birth-weight premature births, and coronary heart disease could be reduced by about 40, 60, and 38%, respectively. For the conditions studied, nearly $20 billion in hospital charges were potentially avoidable with daily use of folic acid and zinc-containing multivitamins by all women of childbearing age and daily vitamin E supplementation by those over 50. PMID:9217432

Secondary Structures of Ubiquitin Ions Soft-Landed onto Self-Assembled Monolayer Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Qichi; Laskin, Julia

2016-06-09

The secondary structures of multiply charged ubiquitin ions soft-landed onto self-assembled monolayer (SAM) surfaces were studied using in situ infrared reflection-absorption spectroscopy (IRRAS). Two charge states of ubiquitin, 5+ and 13+, were mass selected separately from a mixture of different charge states produced by electrospray ionization (ESI). The low 5+ charge state represents a native-like folded state of ubiquitin, while the high 13+ charge state assumes an extended, almost linear conformation. Each of the two charge states was soft-landed onto a CH 3- and COOH-terminated SAM of alkylthiols on gold (HSAM and COOH-SAM). HSAM is a hydrophobic surface known tomore » stabilize helical conformations of soft-landed protonated peptides, whereas COOH-SAM is a hydrophilic surface that preferentially stabilizes β-sheet conformations. IRRAS spectra of the soft-landed ubiquitin ions were acquired as a function of time during and after ion soft-landing. Similar to smaller peptide ions, helical conformations of ubiquitin are found to be more abundant on HSAM, while the relative abundance of β-sheet conformations increases on COOH-SAM. The initial charge state of ubiquitin also has a pronounced effect on its conformation on the surface. Specifically, on both surfaces, a higher relative abundance of helical conformations and lower relative abundance of β-sheet conformations is observed for the 13+ charge state compared to the 5+ charge state. Time-resolved experiments indicate that the α-helical band in the spectrum of the 13+ charge state slowly increases with time on the HSAM surface and decreases in the spectrum of the 13+ charge state on COOH-SAM. These results further support the preference of the hydrophobic HSAM surface toward helical conformations and demonstrate that soft-landed protein ions may undergo slow conformational changes during and after deposition.« less

Comparative study of magnetic ordering in bulk and nanoparticles of Sm0.65Ca0.35MnO3: Magnetization and electron magnetic resonance measurements

NASA Astrophysics Data System (ADS)

Goveas, Lora Rita; Anuradha, K. N.; Bhagyashree, K. S.; Bhat, S. V.

2015-05-01

To explore the effect of size reduction to nanoscale on the hole doped Sm0.65Ca0.35MnO3 compound, dc magnetic measurements and electron magnetic resonance (EMR) were done on bulk and nanoparticle samples in the temperature range 10 ≤ T ≤ 300 K. Magnetization measurement showed that the bulk sample undergoes a charge ordering transition at 240 K and shows a mixed magnetic phase at low temperature. However, the nanosample underwent a ferromagnetic transition at 75 K, and the charge ordered state was destabilized on size reduction down to nanoscale. The low-temperature ferromagnetic component is found to be enhanced in nanoparticles as compared to their bulk counterpart. Interestingly around room temperature, bulk particles show higher magnetization where as at low temperature nanoparticles show higher magnetization. Ferromagnetism in the bulk is due to super exchange where as ferromagnetism in nanoparticles is due to uncompensated spins of the surface layer. Temperature variation of EMR parameters correlates well with the results of magnetic measurements. The magnetic behaviour of the nanoparticles is understood in terms of the core shell scenario.

Evaluation of Alkylamine Modified Pt Nanoparticles as Oxygen Reduction Reaction Electrocatalyst for Fuel Cells via Electrochemical Impedance Spectroscopy.

PubMed

Joshi, Prerna; Okada, Toshihiko; Miyabayashi, Keiko; Miyake, Mikio

2018-05-15

Organically (octyl amine, OA) surface modified electrocatalyst (OA-Pt/CB) was studied for its oxygen reduction reaction (ORR) activity via dc methods and its charge and mass transfer properties were studied via electrochemical impedance spectroscopy (EIS). Comparison with a commercial catalyst (TEC10V30E) with similar Pt content was also carried out. In EIS, both the catalysts showed a single time-constant with an emerging high-frequency semicircle of very small diameter which was fitted using suitable equivalent circuits. The organically modified catalyst showed lower charge-transfer resistance and hence, low polarization resistance in high potential region as compared to the commercial catalyst. The dominance of kinetic processes was observed at 0.925-1.000 V, whereas domination of diffusion based processes was observed at lower potential region for the organic catalyst. No effect due to the presence of carbon was observed in the EIS spectra. Using the hydrodynamic method, higher current penetration depth was obtained for the organically modified catalyst at 1600 rpm. Exchange current density and Tafel slopes for both the electrocatalysts were calculated from the polarization resistance obtained from EIS which was in correlation with the results obtained from dc methods.

The study of surface wetting, nanobubbles and boundary slip with an applied voltage: A review

PubMed Central

Pan, Yunlu; Zhao, Xuezeng

2014-01-01

Summary The drag of fluid flow at the solid–liquid interface in the micro/nanoscale is an important issue in micro/nanofluidic systems. Drag depends on the surface wetting, nanobubbles, surface charge and boundary slip. Some researchers have focused on the relationship between these interface properties. In this review, the influence of an applied voltage on the surface wettability, nanobubbles, surface charge density and slip length are discussed. The contact angle (CA) and contact angle hysteresis (CAH) of a droplet of deionized (DI) water on a hydrophobic polystyrene (PS) surface were measured with applied direct current (DC) and alternating current (AC) voltages. The nanobubbles in DI water and three kinds of saline solution on a PS surface were imaged when a voltage was applied. The influence of the surface charge density on the nanobubbles was analyzed. Then the slip length and the electrostatic force on the probe were measured on an octadecyltrichlorosilane (OTS) surface with applied voltage. The influence of the surface charge on the boundary slip and drag of fluid flow has been discussed. Finally, the influence of the applied voltage on the surface wetting, nanobubbles, surface charge, boundary slip and the drag of liquid flow are summarized. With a smaller surface charge density which could be achieved by applying a voltage on the surface, larger and fewer nanobubbles, a larger slip length and a smaller drag of liquid flow could be found. PMID:25161839

The study of surface wetting, nanobubbles and boundary slip with an applied voltage: A review.

PubMed

Pan, Yunlu; Bhushan, Bharat; Zhao, Xuezeng

2014-01-01

The drag of fluid flow at the solid-liquid interface in the micro/nanoscale is an important issue in micro/nanofluidic systems. Drag depends on the surface wetting, nanobubbles, surface charge and boundary slip. Some researchers have focused on the relationship between these interface properties. In this review, the influence of an applied voltage on the surface wettability, nanobubbles, surface charge density and slip length are discussed. The contact angle (CA) and contact angle hysteresis (CAH) of a droplet of deionized (DI) water on a hydrophobic polystyrene (PS) surface were measured with applied direct current (DC) and alternating current (AC) voltages. The nanobubbles in DI water and three kinds of saline solution on a PS surface were imaged when a voltage was applied. The influence of the surface charge density on the nanobubbles was analyzed. Then the slip length and the electrostatic force on the probe were measured on an octadecyltrichlorosilane (OTS) surface with applied voltage. The influence of the surface charge on the boundary slip and drag of fluid flow has been discussed. Finally, the influence of the applied voltage on the surface wetting, nanobubbles, surface charge, boundary slip and the drag of liquid flow are summarized. With a smaller surface charge density which could be achieved by applying a voltage on the surface, larger and fewer nanobubbles, a larger slip length and a smaller drag of liquid flow could be found.

Profiling charge complementarity and selectivity for binding at the protein surface.

PubMed

Sulea, Traian; Purisima, Enrico O

2003-05-01

A novel analysis and representation of the protein surface in terms of electrostatic binding complementarity and selectivity is presented. The charge optimization methodology is applied in a probe-based approach that simulates the binding process to the target protein. The molecular surface is color coded according to calculated optimal charge or according to charge selectivity, i.e., the binding cost of deviating from the optimal charge. The optimal charge profile depends on both the protein shape and charge distribution whereas the charge selectivity profile depends only on protein shape. High selectivity is concentrated in well-shaped concave pockets, whereas solvent-exposed convex regions are not charge selective. This suggests the synergy of charge and shape selectivity hot spots toward molecular selection and recognition, as well as the asymmetry of charge selectivity at the binding interface of biomolecular systems. The charge complementarity and selectivity profiles map relevant electrostatic properties in a readily interpretable way and encode information that is quite different from that visualized in the standard electrostatic potential map of unbound proteins.

A New Kinetic Simulation Model with Self-Consistent Calculation of Regolith Layer Charging for Moon-Plasma Interactions

NASA Astrophysics Data System (ADS)

Han, D.; Wang, J.

2015-12-01

The moon-plasma interactions and the resulting surface charging have been subjects of extensive recent investigations. While many particle-in-cell (PIC) based simulation models have been developed, all existing PIC simulation models treat the surface of the Moon as a boundary condition to the plasma flow. In such models, the surface of the Moon is typically limited to simple geometry configurations, the surface floating potential is calculated from a simplified current balance condition, and the electric field inside the regolith layer cannot be resolved. This paper presents a new full particle PIC model to simulate local scale plasma flow and surface charging. A major feature of this new model is that the surface is treated as an "interface" between two mediums rather than a boundary, and the simulation domain includes not only the plasma but also the regolith layer and the bedrock underneath it. There are no limitations on the surface shape. An immersed-finite-element field solver is applied which calculates the regolith surface floating potential and the electric field inside the regolith layer directly from local charge deposition. The material property of the regolith layer is also explicitly included in simulation. This new model is capable of providing a self-consistent solution to the plasma flow field, lunar surface charging, the electric field inside the regolith layer and the bedrock for realistic surface terrain. This new model is applied to simulate lunar surface-plasma interactions and surface charging under various ambient plasma conditions. The focus is on the lunar terminator region, where the combined effects from the low sun elevation angle and the localized plasma wake generated by plasma flow over a rugged terrain can generate strongly differentially charged surfaces and complex dust dynamics. We discuss the effects of the regolith properties and regolith layer charging on the plasma flow field, dust levitation, and dust transport.

Acceleration of osteogenesis by using barium titanate piezoelectric ceramic as an implant material

NASA Astrophysics Data System (ADS)

Furuya, K.; Morita, Y.; Tanaka, K.; Katayama, T.; Nakamachi, E.

2011-04-01

As bone has piezoelectric properties, it is expected that activity of bone cells and bone formation can be accelerated by applying piezoelectric ceramics to implants. Since lead ions, included in ordinary piezoelectric ceramics, are harmful, a barium titanate (BTO) ceramic, which is a lead-free piezoelectric ceramic, was used in this study. The purpose of this study was to investigate piezoelectric effects of surface charge of BTO on cell differentiation under dynamic loading in vitro. Rat bone marrow cells seeded on surfaces of BTO ceramics were cultured in culture medium supplemented with dexamethasone, β-glycerophosphate and ascorbic acid while a dynamic load was applied to the BTO ceramics. After 10 days of cultivation, the cell layer and synthesized matrix on the BTO surfaces were scraped off, and then DNA content, alkaline phosphtase (ALP) activity and calcium content were measured, to evaluate osteogenic differentiation. ALP activity on the charged BTO surface was slightly higher than that on the non-charged BTO surface. The amount of calcium on the charged BTO surface was also higher than that on the non-charged BTO surface. These results showed that the electric charged BTO surface accelerated osteogenesis.

Adsorption of hydrophobin on different self-assembled monolayers: the role of the hydrophobic dipole and the electric dipole.

PubMed

Peng, Chunwang; Liu, Jie; Zhao, Daohui; Zhou, Jian

2014-09-30

In this work, the adsorptions of hydrophobin (HFBI) on four different self-assembled monolayers (SAMs) (i.e., CH3-SAM, OH-SAM, COOH-SAM, and NH2-SAM) were investigated by parallel tempering Monte Carlo and molecular dynamics simulations. Simulation results indicate that the orientation of HFBI adsorbed on neutral surfaces is dominated by a hydrophobic dipole. HFBI adsorbs on the hydrophobic CH3-SAM through its hydrophobic patch and adopts a nearly vertical hydrophobic dipole relative to the surface, while it is nearly horizontal when adsorbed on the hydrophilic OH-SAM. For charged SAM surfaces, HFBI adopts a nearly vertical electric dipole relative to the surface. HFBI has the narrowest orientation distribution on the CH3-SAM, and thus can form an ordered monolayer and reverse the wettability of the surface. For HFBI adsorption on charged SAMs, the adsorption strength weakens as the surface charge density increases. Compared with those on other SAMs, a larger area of the hydrophobic patch is exposed to the solution when HFBI adsorbs on the NH2-SAM. This leads to an increase of the hydrophobicity of the surface, which is consistent with the experimental results. The binding of HFBI to the CH3-SAM is mainly through hydrophobic interactions, while it is mediated through a hydration water layer near the surface for the OH-SAM. For the charged SAM surfaces, the adsorption is mainly induced by electrostatic interactions between the charged surfaces and the oppositely charged residues. The effect of a hydrophobic dipole on protein adsorption onto hydrophobic surfaces is similar to that of an electric dipole for charged surfaces. Therefore, the hydrophobic dipole may be applied to predict the probable orientations of protein adsorbed on hydrophobic surfaces.

Reduced graphene oxide-ZnO self-assembled films: tailoring the visible light photoconductivity by the intrinsic defect states in ZnO.

PubMed

Kavitha, M K; Gopinath, Pramod; John, Honey

2015-06-14

ZnO is a wide direct bandgap semiconductor; its absorption can be tuned to the visible spectral region by controlling the intrinsic defect levels. Combining graphene with ZnO can improve its performance by photo-induced charge separation by ZnO and electronic transport through graphene. When reduced graphene oxide-ZnO is prepared by a hydrothermal method, the photophysical studies indicate that oxygen vacancy defect states are healed out by diffusion of oxygen from GO to ZnO during its reduction. Because of the passivation of oxygen vacancies, the visible light photoconductivity of the hybrid is depleted, compared to pure ZnO. In order to overcome this reduction in photocurrent, a photoelectrode is fabricated by layer-by-layer (LBL) self-assembly of ZnO and reduced graphene oxide. The multilayer films are fabricated by the electrostatic LBL self-assembly technique using negatively charged poly(sodium 4-styrene sulfonate)-reduced graphene oxide (PSS-rGO) and positively charged polyacrylamide-ZnO (PAM-ZnO) as building blocks. The multilayer films fabricated by this technique will be highly interpenetrating; it will enhance the interaction between the ZnO and rGO perpendicular to the electrode surface. Upon illumination under bias voltage defect assisted excitation occurs in ZnO and the photogenerated charge carriers can transfer to graphene. The electron transferred to graphene sheets can recombine in two ways; either it can recombine with the holes in the valence band of ZnO in its bilayer or the ZnO in the next bilayer. This type of tunnelling of electrons from graphene to the successive bilayers will result in efficient charge transfer. This transfer and propagation of electron will enhance as the number of bilayers increases, which in turn improve the photocurrent of the multilayer films. Therefore this self-assembly technique is an effective approach to fabricate semiconductor-graphene films with excellent conductivity.

Effects of oxygen radicals in low-pressure surface-wave plasma on sterilization

NASA Astrophysics Data System (ADS)

Nagatsu, Masaaki; Terashita, Fumie; Nonaka, Hiroyuki; Xu, Lei; Nagata, Toshi; Koide, Yukio

2005-05-01

The effects of oxygen radicals on sterilization were studied using a 2.45GHz surface-wave oxygen plasma. A population of 1.5×106 Bacillus stearothermophilus spores was irradiated for 3min or more with oxygen plasma, generated at pressures between 6 and 14Pa. The decimal reduction value (D value), a measure of the effectiveness of sterilization, was determined to be about 15-25s. Using only oxygen radicals, excluding all charged particles, the 1.5×106 spores were sterilized with a D value of 30-45s after 5min or more of irradiation. On scanning electron microscopy, the length and width of the spores changed significantly due to chemical etching by oxygen radicals.

Determination of Protein Surface Hydration by Systematic Charge Mutations

NASA Astrophysics Data System (ADS)

Yang, Jin; Jia, Menghui; Qin, Yangzhong; Wang, Dihao; Pan, Haifeng; Wang, Lijuan; Xu, Jianhua; Zhong, Dongping; Dongping Zhong Collaboration; Jianhua Xu Collaboration

Protein surface hydration is critical to its structural stability, flexibility, dynamics and function. Recent observations of surface solvation on picosecond time scales have evoked debate on the origin of such relatively slow motions, from hydration water or protein charged sidechains, especially with molecular dynamics simulations. Here, we used a unique nuclease with a single tryptophan as a local probe and systematically mutated neighboring three charged residues to differentiate the contributions from hydration water and charged sidechains. By mutations of alternative one and two and all three charged residues, we observed slight increases in the total tryptophan Stokes shifts with less neighboring charged residue(s) and found insensitivity of charged sidechains to the relaxation patterns. The dynamics is correlated with hydration water relaxation with the slowest time in a dense charged environment and the fastest time at a hydrophobic site. On such picosecond time scales, the protein surface motion is restricted. The total Stokes shifts are dominantly from hydration water relaxation and the slow dynamics is from water-driven relaxation, coupled with local protein fluctuations.

Threshold-Based Random Charging Scheme for Decentralized PEV Charging Operation in a Smart Grid.

PubMed

Kwon, Ojin; Kim, Pilkee; Yoon, Yong-Jin

2016-12-26

Smart grids have been introduced to replace conventional power distribution systems without real time monitoring for accommodating the future market penetration of plug-in electric vehicles (PEVs). When a large number of PEVs require simultaneous battery charging, charging coordination techniques have become one of the most critical factors to optimize the PEV charging performance and the conventional distribution system. In this case, considerable computational complexity of a central controller and exchange of real time information among PEVs may occur. To alleviate these problems, a novel threshold-based random charging (TBRC) operation for a decentralized charging system is proposed. Using PEV charging thresholds and random access rates, the PEVs themselves can participate in the charging requests. As PEVs with a high battery state do not transmit the charging requests to the central controller, the complexity of the central controller decreases due to the reduction of the charging requests. In addition, both the charging threshold and the random access rate are statistically calculated based on the average of supply power of the PEV charging system that do not require a real time update. By using the proposed TBRC with a tolerable PEV charging degradation, a 51% reduction of the PEV charging requests is achieved.

Threshold-Based Random Charging Scheme for Decentralized PEV Charging Operation in a Smart Grid

PubMed Central

Kwon, Ojin; Kim, Pilkee; Yoon, Yong-Jin

2016-01-01

Smart grids have been introduced to replace conventional power distribution systems without real time monitoring for accommodating the future market penetration of plug-in electric vehicles (PEVs). When a large number of PEVs require simultaneous battery charging, charging coordination techniques have become one of the most critical factors to optimize the PEV charging performance and the conventional distribution system. In this case, considerable computational complexity of a central controller and exchange of real time information among PEVs may occur. To alleviate these problems, a novel threshold-based random charging (TBRC) operation for a decentralized charging system is proposed. Using PEV charging thresholds and random access rates, the PEVs themselves can participate in the charging requests. As PEVs with a high battery state do not transmit the charging requests to the central controller, the complexity of the central controller decreases due to the reduction of the charging requests. In addition, both the charging threshold and the random access rate are statistically calculated based on the average of supply power of the PEV charging system that do not require a real time update. By using the proposed TBRC with a tolerable PEV charging degradation, a 51% reduction of the PEV charging requests is achieved. PMID:28035963

Phosphorus solubility of agricultural soils: a surface charge and phosphorus-31 NMR speciation study

USDA-ARS?s Scientific Manuscript database

We investigated ten soils from six states in United States to determine the relationship between potentiometric titration derived soil surface charge and Phosphorus-31 (P) nuclear magnetic resonance (NMR) speciation with the concentration of water-extractable P (WEP). The surface charge value at the...

Charge gradient microscopy

DOEpatents

Roelofs, Andreas; Hong, Seungbum

2018-02-06

A method for rapid imaging of a material specimen includes positioning a tip to contact the material specimen, and applying a force to a surface of the material specimen via the tip. In addition, the method includes moving the tip across the surface of the material specimen while removing electrical charge therefrom, generating a signal produced by contact between the tip and the surface, and detecting, based on the data, the removed electrical charge induced through the tip during movement of the tip across the surface. The method further includes measuring the detected electrical charge.

Effects of the March 2015 solar eclipse on near-surface atmospheric electricity.

PubMed

Bennett, A J

2016-09-28

Measurements of atmospheric electrical and standard meteorological parameters were made at coastal and inland sites in southern England during the 20 March 2015 partial solar eclipse. Clear evidence of a reduction in air temperature resulting from the eclipse was found at both locations, despite one of them being overcast during the entire eclipse. The reduction in temperature was expected to affect the near-surface electric field (potential gradient (PG)) through a reduction in turbulent transfer of space charge. No such effect could be unambiguously confirmed, however, with variability in PG and air-Earth current during the eclipse being comparable to pre- and post-eclipse conditions. The already low solar radiation for this latitude, season and time of day was likely to have contributed to the reduced effect of the eclipse on atmospheric electricity through boundary layer stability. The absence of a reduction in mean PG shortly after time of maximum solar obscuration, as observed during eclipses at lower geomagnetic latitude, implied that there was no significant change in atmospheric ionization from cosmic rays above background variability. This finding was suggested to be due to the relative importance of cosmic rays of solar and galactic origin at geomagnetic mid-latitudes.This article is part of the themed issue 'Atmospheric effects of solar eclipses stimulated by the 2015 UK eclipse'. © 2016 The Author(s).

Activation of CO2 by supported Cu clusters.

PubMed

Iyemperumal, Satish Kumar; Deskins, N Aaron

2017-11-01

Catalytic reduction of carbon dioxide to useful chemicals is a potent way to mitigate this greenhouse gas, but the challenge lies in finding active reduction catalysts. Using density functional theory we studied CO 2 activation over TiO 2 -supported Cu clusters of size 1-4 atoms. The linear to bent transformation of CO 2 is necessary for activation, and we found that all the clusters stabilized bent CO 2 , along with a significant gain of electrons on the CO 2 (indicative of activation). On all the TiO 2 supported Cu clusters, the interfacial sites were found to stabilize the bent CO 2 adsorption, where the active site of adsorption on Cu dimer, trimer and tetramer was on the Cu atom farthest away from the TiO 2 surface. Particularly, the Cu dimer stabilized bent CO 2 very strongly, although this species was found to be unstable on the surface. A synthesis technique that could stabilize the Cu dimer could therefore lead to a very active catalyst. Furthermore we found (using vibrational and charge analysis) that the active sites for the CO 2 activation predominantly had 0 and +1 oxidation states; the oxidation state of Cu is known to directly affect CO 2 reduction activity. Our study shows TiO 2 -supported small Cu clusters can be active catalysts for CO 2 reduction and also provides further motivation for theoretical and experimental studies of metal clusters.

Variable Charge Soils: Mineralogy and Chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qafoku, Nik; Van Ranst, Eric; Noble, Andrew

2003-11-01

Soils rich in particles with amphoteric surface properties in the Oxisols, Ultisols, Alfisols, Spodosols and Andisols orders (1) are considered variable charge soils (2). The term “variable charge” is used to describe organic and inorganic soil constituents with reactive surface groups whose charge varies with pH, ionic concentration and composition of the soil solution. Such groups are the surface carboxyl, phenolic and amino functional groups of organic materials in soils, and surface hydroxyl groups of Fe and Al oxides, allophane and imogolite. The hydroxyl surface groups are also present on edges of some phyllosilicate minerals such as kaolinite, mica, andmore » hydroxyl-interlayered vermiculite. The variable charge is developed on the surface groups as a result of adsorption or desorption of ions that are constituents of the solid phase, i.e., H+, and the adsorption or desorption of solid-unlike ions that are not constituents of the solid. Highly weathered soils usually undergo isoeletric weathering and reach a “zero net charge” stage during their development. They have a slightly acidic to acidic soil solution pH, which is close to either point of zero net charge (PZNC) (3) or point of zero salt effect (PZSE) (3). They are characterized by high abundances of minerals with a point of zero net proton charge (PZNPC) (3) at neutral and slightly basic pHs; the most important being Fe and Al oxides and allophane. Under acidic conditions, the surfaces of these minerals are net positively charged. In contrast, the surfaces of permanent charge phyllosilicates are negatively charged regardless of ambient conditions. Variable charge soils therefore, are heterogeneous charge systems. The coexistence and interactions of oppositely charged surfaces or particles confers a different pattern of physical and chemical behavior on the soil, relatively to a homogeneously charged system of temperate regions. In some variable charge soils (Oxisols and some Ultisols developed on ferromagnesian-rich parent materials) the surfaces of phyllosilicates are coated to a lesser or greater extent by amorphous or crystalline, oppositely charged nanoparticles of Fe and Al oxides. These coatings exhibit a high reactive surface area and help cementing larger particles with one another. As a result of these electrostatic interactions, stable microaggregates that are difficult to disperse are formed in variable charge soils. Most of highly weathered soils have reached the “advanced stage” of Jackson-Sherman weathering sequence that is characterized by the removal of Na, K, Ca, Mg, and Fe(II), the presence of Fe and Al polymers, and very dilute soil solutions with an ionic strength (IS) of less than 1 mmol L-1. The inter-penetration or overlapping of the diffuse double layers on oppositely charged surfaces may occur in these dilute systems. These diffuse layer interactions may affect the magnitude of the effective charge, i.e., the counter-ion charge (4). In addition, salt adsorption, which is defined as the simultaneous adsorption in equivalent amounts of the cation and anion of an electrolyte with no net release of other ions into the soil solution, appears to be a common phenomenon in these soils. They act as cation- and anion-exchangers and as salt-sorbers. The magnitude of salt adsorption depends strongly on initial IS in the soil solution and the presence in appreciable amounts of oppositely charged surfaces. Among the authors that have made illustrious contributions towards a better understanding of these fascinating soil systems are S. Matson, R.K. Schofield, van Olphen, M.E. Sumner, G.W. Thomas, G.P. Gillman, G. Uehara, B.K.G. Theng, K. Wada, N.J. Barrow, J.W. Bowden, R.J. Hunter and G. Sposito. This entry is mainly based on publications by these authors.« less

Effect of Surfaces on Amyloid Fibril Formation

PubMed Central

Moores, Bradley; Drolle, Elizabeth; Attwood, Simon J.; Simons, Janet; Leonenko, Zoya

2011-01-01

Using atomic force microscopy (AFM) we investigated the interaction of amyloid beta (Aβ) (1–42) peptide with chemically modified surfaces in order to better understand the mechanism of amyloid toxicity, which involves interaction of amyloid with cell membrane surfaces. We compared the structure and density of Aβ fibrils on positively and negatively charged as well as hydrophobic chemically-modified surfaces at physiologically relevant conditions. We report that due to the complex distribution of charge and hydrophobicity amyloid oligomers bind to all types of surfaces investigated (CH3, COOH, and NH2) although the charge and hydrophobicity of surfaces affected the structure and size of amyloid deposits as well as surface coverage. Hydrophobic surfaces promote formation of spherical amorphous clusters, while charged surfaces promote protofibril formation. We used the nonlinear Poisson-Boltzmann equation (PBE) approach to analyze the electrostatic interactions of amyloid monomers and oligomers with modified surfaces to complement our AFM data. PMID:22016789

Shedding PEG Palisade by Temporal Photostimulation and Intracellular Reducing Milieu for Facilitated Intracellular Trafficking and DNA Release.

PubMed

Wang, Tieyan; Chen, Qixian; Lu, Hongguang; Li, Wei; Li, Zaifen; Ma, Jianbiao; Gao, Hui

2016-08-17

The dilemma of poly(ethylene glycol) surface modification (PEGylation) inspired us to develop an intracellularly sheddable PEG palisade for synthetic delivery systems. Here, we attempted to conjugate PEG to polyethylenimine (PEI) through tandem linkages of disulfide-bridge susceptible to cytoplasmic reduction and an azobenzene/cyclodextrin inclusion complex responsive to external photoirradiation. The subsequent investigations revealed that facile PEG detachment could be achieved in endosomes upon photoirradiation, consequently engendering exposure of membrane-disruptive PEI for facilitated endosome escape. The liberated formulation in the cytosol was further subjected to complete PEG detachment relying on disulfide cleavage in the reductive cytosol, thus accelerating dissociation of electrostatically assembled PEI/DNA polyplex to release DNA by means of polyion exchange reaction with intracellularly charged species, ultimately contributing to efficient gene expression.

Parallel tempering Monte Carlo simulations of lysozyme orientation on charged surfaces

NASA Astrophysics Data System (ADS)

Xie, Yun; Zhou, Jian; Jiang, Shaoyi

2010-02-01

In this work, the parallel tempering Monte Carlo (PTMC) algorithm is applied to accurately and efficiently identify the global-minimum-energy orientation of a protein adsorbed on a surface in a single simulation. When applying the PTMC method to simulate lysozyme orientation on charged surfaces, it is found that lysozyme could easily be adsorbed on negatively charged surfaces with "side-on" and "back-on" orientations. When driven by dominant electrostatic interactions, lysozyme tends to be adsorbed on negatively charged surfaces with the side-on orientation for which the active site of lysozyme faces sideways. The side-on orientation agrees well with the experimental results where the adsorbed orientation of lysozyme is determined by electrostatic interactions. As the contribution from van der Waals interactions gradually dominates, the back-on orientation becomes the preferred one. For this orientation, the active site of lysozyme faces outward, which conforms to the experimental results where the orientation of adsorbed lysozyme is co-determined by electrostatic interactions and van der Waals interactions. It is also found that despite of its net positive charge, lysozyme could be adsorbed on positively charged surfaces with both "end-on" and back-on orientations owing to the nonuniform charge distribution over lysozyme surface and the screening effect from ions in solution. The PTMC simulation method provides a way to determine the preferred orientation of proteins on surfaces for biosensor and biomaterial applications.

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary system and enhanced overlapping of diffuse layers on these oppositely charged surfaces compared with other two binary systems. In conclusion, the overlapping of diffuse layers occurred between positively charged Fe/Al oxides and rice roots, which led to neutralization of opposite charge and affected adsorption and desorption of ions onto and from the charged surfaces of Fe/Al oxides and rice roots.

Effect of electrical polarization of hydroxyapatite ceramics on new bone formation.

PubMed

Itoh, S; Nakamura, S; Kobayashi, T; Shinomiya, K; Yamashita, K; Itoh, S

2006-03-01

Large surface charges can be induced on hydroxyapatite (HAp) ceramics by proton transport polarization, but this does not affect beta-tricalcium phosphate (TCP) because of its low polarizability. We wished to examine differences in osteogenic cell activity and new bone growth between positively or negatively surface-charged HAp and HAp/TCP plates using a calvarial bone defect model. In the first group of rats, test pieces were placed with their positively charged surfaces face down on the dura mater. In the second group, test pieces were placed with their negatively charged surfaces face down on the dura mater. A third group received noncharged test pieces. Histological examination, including enzymatic staining for osteoblasts and osteoclasts, was carried out. While no bone formation was observed at the pericranium, direct bone formation on the cranial bone debris and new bone growth expanded from the margins of the sites of injury to bridge across both the positively and negatively charged surfaces of HAp and HAp/TCP plates occurred. Electrical polarization of implanted plates, including positive charge, led to enhanced osteoblast activity, though decreased osteoclast activity was seen on the positively charged plate surface. Thus, polarization of HAp ceramics may modulate new bone formation and resorption.

Formation of positively charged gold nanoparticle monolayers on silica sensors.

PubMed

Oćwieja, Magdalena; Maciejewska-Prończuk, Julia; Adamczyk, Zbigniew; Roman, Maciej

2017-09-01

Formation of positively charged gold nanoparticle monolayers on the Si/SiO 2 was studied under in situ conditions using quartz microbalance (QCM). The gold nanoparticles were synthesized in a chemical reduction method using sodium borohydride as reducing agent. Cysteamine hydrochloride was applied to generate a positive surface charge of nanoparticles. The micrographs obtained from transmission electron microscopy (TEM) revealed that the average size of nanoparticles was equal to 12±3nm. The stability of nanoparticle suspensions under controlled pH and ionic strength was determined by dynamic light scattering (DLS). The electrophoretic mobility measurements showed that the zeta potential of nanoparticles was positive, decreasing with ionic strength and pH from 56mV at pH 4.2 and I=10 -4 M to 22mV at pH 8.3 and I=3×10 -3 M. The surface enhanced Raman spectroscopy (SERS) confirmed chemisorption of cysteamine on nanoparticles and the contribution of amine moieties in the generation of nanoparticle charge. The influence of suspension concentration, ionic strength and flow rate on the kinetics of nanoparticle deposition on the sensors was quantitatively determined. It was confirmed that the deposition for the low coverage regime is governed by the bulk mass transfer that results in a linear increase of the coverage with time. The significant increase in the maximum coverage of gold monolayers with ionic strength was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. Moreover, the hydratation of formed monolayers, their structure and the stability were determined by the comparison of the QCM results with those obtained by AFM and SEM. The experimental data were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model that considers the bulk and surface transfer steps in a rigorous way. The obtained results are useful for a facile fabrication of gold nanoparticle-based biosensors capable to bind target molecules via available amine moieties. Copyright © 2017 Elsevier Inc. All rights reserved.

The crystal structure of Haloferax volcanii proliferating cell nuclear antigen reveals unique surface charge characteristics due to halophilic adaptation

PubMed Central

Winter, Jody A; Christofi, Panayiotis; Morroll, Shaun; Bunting, Karen A

2009-01-01

Background The high intracellular salt concentration required to maintain a halophilic lifestyle poses challenges to haloarchaeal proteins that must stay soluble, stable and functional in this extreme environment. Proliferating cell nuclear antigen (PCNA) is a fundamental protein involved in maintaining genome integrity, with roles in both DNA replication and repair. To investigate the halophilic adaptation of such a key protein we have crystallised and solved the structure of Haloferax volcanii PCNA (HvPCNA) to a resolution of 2.0 Å. Results The overall architecture of HvPCNA is very similar to other known PCNAs, which are highly structurally conserved. Three commonly observed adaptations in halophilic proteins are higher surface acidity, bound ions and increased numbers of intermolecular ion pairs (in oligomeric proteins). HvPCNA possesses the former two adaptations but not the latter, despite functioning as a homotrimer. Strikingly, the positive surface charge considered key to PCNA's role as a sliding clamp is dramatically reduced in the halophilic protein. Instead, bound cations within the solvation shell of HvPCNA may permit sliding along negatively charged DNA by reducing electrostatic repulsion effects. Conclusion The extent to which individual proteins adapt to halophilic conditions varies, presumably due to their diverse characteristics and roles within the cell. The number of ion pairs observed in the HvPCNA monomer-monomer interface was unexpectedly low. This may reflect the fact that the trimer is intrinsically stable over a wide range of salt concentrations and therefore additional modifications for trimer maintenance in high salt conditions are not required. Halophilic proteins frequently bind anions and cations and in HvPCNA cation binding may compensate for the remarkable reduction in positive charge in the pore region, to facilitate functional interactions with DNA. In this way, HvPCNA may harness its environment as opposed to simply surviving in extreme halophilic conditions. PMID:19698123

PALS and SPM/EFM investigation of charged nanoporous electret films

NASA Astrophysics Data System (ADS)

Chiang, Dar-Ming; Liu, Wen-Liang; Chen, Jen-Luan; Susuki, Ryoichi

2005-08-01

The electret properties of nanoporous Teflon-FEP films, fabricated by the super-critical fluids method and charged by the corona method at room temperature, are investigated. PALS and SAXS are applied first to examine the charge characteristics of a free volume of electret materials. The topography and surface charges of electret materials are determined by scanning probe microscopy and electric field microscopy, respectively. The experimental results reveal that the interior surface areas of the pores of the electret materials influence the retention and stability of charge. Initial and aged surface charge was increased by factors of two and ten, with and without nanoporous Teflon-FEP films, respectively.

Solar Wind Access to Lunar Polar Craters: Feedback Between Surface Charging and Plasma Expansion

NASA Technical Reports Server (NTRS)

Zimmerman, M. I.; Farrell, W. M.; Stubbs, T. J.; Halekas, J. S.; Jackson, T. L.

2011-01-01

Determining the plasma environment within permanently shadowed lunar craters is critical to understanding local processes such as surface charging, electrostatic dust transport, volatile sequestration, and space weathering. In order to investigate the nature of this plasma environment, the first two-dimensional kinetic simulations of solar wind expansion into a lunar crater with a self-consistent plasma-surface interaction have been undertaken. The present results reveal how the plasma expansion into a crater couples with the electrically-charged lunar surface to produce a quasi-steady wake structure. In particular, there is a negative feedback between surface charging and ambipolar wake potential that allows an equilibrium to be achieved, with secondary electron emission strongly moderating the process. A range of secondary electron yields is explored, and two distinct limits are highlighted in which either surface charging or ambipoiar expansion is responsible for determining the overall wake structure.

Microelectrophoretic study of calcium oxalate monohydrate in macromolecular solutions

NASA Technical Reports Server (NTRS)

Curreri, P. A.; Onoda, G. Y., Jr.; Finlayson, B.

1987-01-01

Electrophoretic mobilities were measured for calcium oxalate monohydrate (COM) in solutions containing macromolecules. Two mucopolysaccharides (sodium heparin and chondroitin sulfate) and two proteins (positively charged lysozyme and negatively charged bovine serum albumin) were studied as adsorbates. The effects of pH, calcium oxalate surface charge (varied by calcium or oxalate ion activity), and citrate concentration were investigated. All four macromolecules showed evidence for adsorption. The macromolecule concentrations needed for reversing the surface charge indicated that the mucopolysaccharides have greater affinity for the COM surface than the proteins. Citrate ions at high concentrations appear to compete effectively with the negative protein for surface sites but show no evidence for competing with the positively charged protein.

The influence of the carbonate species on LiNi0.8Co0.15Al0.05O2 surfaces for all-solid-state lithium ion battery performance

NASA Astrophysics Data System (ADS)

Visbal, Heidy; Fujiki, Satoshi; Aihara, Yuichi; Watanabe, Taku; Park, Youngsin; Doo, Seokgwang

2014-12-01

The influence of selected carbonate species on LiNi0.8Co0.15Al0.05O2 (NCA) surface for all-solid-state lithium-ion battery (ASSB) with a sulfide based solid electrolyte was studied for its electrochemical properties, structural stabilities, and surface characteristics. The rated discharge performance improved with the reduction of the carbonate concentration on the NCA surface due to the decrease of the interface resistance. The species and coordination of the adsorbed carbonates on the NCA surface were analyzed by diffuse reflectance Fourier transformed infrared (DRIFT) spectroscopy. The coordination of the adsorbed carbonate anion was determined based on the degree of splitting of the ν3(CO) stretching vibrations. It is found that the surface carbonate species exists in an unidentate coordination on the surface. They react with the sulfide electrolyte to form an irreversible passivation layer. This layer obstructs the charge transfer process at the cathode/electrolyte interface, and results in the rise of the interface resistance and drop of the rated discharge capability.

Electrostatic cloaking of surface structure for dynamic wetting

NASA Astrophysics Data System (ADS)

Shiomi, Junichiro; Nita, Satoshi; Do-Quang, Minh; Wang, Jiayu; Chen, Yu-Chung; Suzuki, Yuji; Amberg, Gustav

2017-11-01

Dynamic wetting problems are fundamental to the understanding of the interaction between liquids and solids. Even in a superficially simple experimental situation, such as a droplet spreading over a dry surface, the result may depend not only on the liquid properties but also strongly on the substrate-surface properties; even for macroscopically smooth surfaces, the microscopic geometrical roughness can be important. In addition, as surfaces may often be naturally charged, or electric fields are used to manipulate fluids, electric effects are crucial components that influence wetting phenomena. Here we investigate the interplay between electric forces and surface structures in dynamic wetting. While surface microstructures can significantly hinder the spreading, we find that the electrostatics can ``cloak'' the microstructures, i.e. deactivate the hindering. We identify the physics in terms of reduction in contact-line friction, which makes the dynamic wetting inertial force dominant and insensitive to the substrate properties. This work was financially supported in part by, the Japan Society for the Promotion of Science, Swedish Governmental Agency for Innovation Systems, and the Japan Science and Technology Agency.

Photoluminescence and capacitance voltage characterization of GaAs surface passivated by an ultrathin GaN interface control layer

NASA Astrophysics Data System (ADS)

Anantathanasarn, Sanguan; Hasegawa, Hideki

2002-05-01

A novel surface passivation technique for GaAs using an ultrathin GaN interface control layer (GaN ICL) formed by surface nitridation was characterized by ultrahigh vacuum (UHV) photoluminescence (PL) and capacitance-voltage ( C- V) measurements. The PL quantum efficiency was dramatically enhanced after being passivated by the GaN ICL structure, reaching as high as 30 times of the initial clean GaAs surface. Further analysis of PL data was done by the PL surface state spectroscopy (PLS 3) simulation technique. PL and C- V results are in good agreement indicating that ultrathin GaN ICL reduces the gap states and unpins the Fermi level, realizing a wide movement of Fermi level within the midgap region and reduction of the effective surface recombination velocity by a factor of 1/60. GaN layer also introduced a large negative surface fixed charge of about 10 12 cm -2. A further improvement took place by depositing a Si 3N 4 layer on GaN ICL/GaAs structure.

Structural charge site influence on the interlayer hydration of expandable three-sheet clay minerals

USGS Publications Warehouse

Kerns, Raymond L.; Mankin, Charles J.

1968-01-01

Previous investigations have demonstrated the influences of interlayer cation composition, relative humidity, temperature, and magnitude of interlayer surface charge on the interlayer hydration of montmorillonites and vermiculites. It has been suggested that the sites of layer charge deficiencies may also have an influence upon the amount of hydration that can take place in the interlayers of expandable clay minerals. If the interlayer cation-to-layer bonds are considered as ideally electrostatic, the magnitude of the forces resisting expansion may be expressed as a form of Coulomb's law. If this effect is significant, expandable structures in which the charge-deficiency sites are predominantly in the tetrahedral sheet should have less pronounced swelling properties than should structures possessing charge deficiencies located primarily in the octahedral sheet.Three samples that differed in location of layer charge sites were selected for study. An important selection criterion was a non-correlation between tetrahedral charge sites and high surface-charge density, and between octahedral charge sites and low surface-charge density.The effects of differences in interlayer cation composition were eliminated by saturating portions of each sample with the same cations. Equilibrium (001) d values at controlled constant humidities were used as a measure of the relative degree of interlayer hydration.Although no correlation could be made between the degree of interlayer hydration and total surface-charge density, the investigation does not eliminate total surface-charge density as being significant to the swelling properties of three-sheet clay-mineral structures. The results do indicate a correlation between more intense expandability and predominance of charge deficiencies in the octahedral sheet. Conversely, less intense swelling behavior is associated with predominantly tetrahedral charge deficiencies.

Detailed studies of a high-capacity electrode material for rechargeable batteries, Li2MnO3-LiCo(1/3)Ni(1/3)Mn(1/3)O2.

PubMed

Yabuuchi, Naoaki; Yoshii, Kazuhiro; Myung, Seung-Taek; Nakai, Izumi; Komaba, Shinichi

2011-03-30

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

The role of surface charge on the uptake and biocompatibility of hydroxyapatite nanoparticles with osteoblast cells

PubMed Central

Chen, Liang; Mccrate, Joseph M.; Lee, James C-M.; Li, Hao

2011-01-01

The objective of this study is to evaluate the effect of hydroxyapatite (HAP) nanoparticles with different surface charges on the cellular uptake behavior and in vitro cell viability and proliferation of MC3T3-E1 cell lines (osteoblast). The nanoparticles surface charge was varied by the surface modification with two carboxylic acids: 12-aminododecanoic acid (positive) and dodecanedioic acid (negative). The untreated HAP nanoparticles and dodecanoic acid modified HAP nanoparticles (neutral) were used as the control. X-ray diffraction (XRD) revealed that surface modifications by the three carboxylic acids did not change the crystal structure of HAP nanoparticles; Fourier transform infrared spectroscopy (FTIR) confirmed the adsorption and binding of the carboxylic acids on HAP nanoparticle surface; and zeta potential measurement confirmed that the chemicals successfully modified the surface charge of HAP nanoparticles in water based solution. Transmission electron microscopy (TEM) images showed that positively charged, negatively charged and untreated HAP nanoparticles, with similar size and shape, all penetrated into the cells and cells had more uptake of HAP nanoparticles with positive charge compared to those with negative charge, which might be attributed to the attractive or repulsive interaction between the negatively charged cell membrane and positively/negatively charged HAP nanoparticles. The neutral HAP nanoparticles could not penetrate cell membrane due to the larger size. MTT assay and LDH assay results indicated that as compared with the polystyrene control, greater cell viability and cell proliferation were measured on MC3T3-E1 cells treated with the three kinds of the HAP nanoparticles (neutral, positive, and untreated), among which positively charged HAP nanoparticles shows strongest improvement for cell viability and cell proliferation. In summary, the surface charge of HAP nanoparticles can be modified to influence the cellular uptake of HAP nanoparticles and the different uptake also influence the behavior of cells. These in-vitro results may also provide useful information for investigations of HAP nanoparticles applications in the gene delivery and intracellular drug delivery. PMID:21289408

A Spacecraft Charging Capability for SXTF.

DTIC Science & Technology

1979-01-17

surfaces can charge up. ’Iiiis differential charging of satellite surfaces can cause vacutum sparks , and dielectric breakdowns, and wi 11 effect the S...times required to reach steady charge state in the spacecraft internal dielectrics upon electron irradiation. In space , typical times (order of magni...WORDS (Continue on reverse side it necessary end Identify by block nunmber) Spacecraft charging Dielectric breakdown SGEMP Electron accelerators

Precise control of surface electrostatic forces on polymer brush layers with opposite charges for resistance to protein adsorption.

PubMed

Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

2016-10-01

Various molecular interaction forces are generated during protein adsorption process on material surfaces. Thus, it is necessary to control them to suppress protein adsorption and the subsequent cell and tissue responses. A series of binary copolymer brush layers were prepared via surface-initiated atom transfer radical polymerization, by mixing the cationic monomer unit and anionic monomer unit randomly in various ratios. Surface characterization revealed that the constructed copolymer brush layers exhibited an uniform super-hydrophilic nature and different surface potentials. The strength of the electrostatic interaction forces operating on these mixed-charge copolymer brush surfaces was evaluated quantitatively using force-versus-distance (f-d) curve measurements by atomic force microscopy (AFM) and probes modified by negatively charged carboxyl groups or positively charged amino groups. The electrostatic interaction forces were determined based on the charge ratios of the copolymer brush layers. Notably, the surface containing equivalent cationic/anionic monomer units hardly interacted with both the charged groups. Furthermore, the protein adsorption force and the protein adsorption mass on these surfaces were examined by AFM f-d curve measurement and surface plasmon resonance measurement, respectively. To clarify the influence of the electrostatic interaction on the protein adsorption behavior on the surface, three kinds of proteins having negative, positive, and relatively neutral net charges under physiological conditions were used in this study. We quantitatively demonstrated that the amount of adsorbed proteins on the surfaces would have a strong correlation with the strength of surface-protein interaction forces, and that the strength of surface-protein interaction forces would be determined from the combination between the properties of the electrostatic interaction forces on the surfaces and the charge properties of the proteins. Especially, the copolymer brush surface composed of equivalent cationic/anionic monomer units exhibited no significant interaction forces, and dramatically suppressed the adsorption of proteins regardless of their charge properties. We conclude that the established methodology could elucidate relationship between the protein adsorption behavior and molecular interaction, especially the electrostatic interaction forces, and demonstrated that the suppression of the electrostatic interactions with the ionic functional groups would be important for the development of new polymeric biomaterials with a high repellency of protein adsorption. Copyright © 2016 Elsevier Ltd. All rights reserved.

The role of interfacial water layer in atmospherically relevant charge separation

NASA Astrophysics Data System (ADS)

Bhattacharyya, Indrani

Charge separation at interfaces is important in various atmospheric processes, such as thunderstorms, lightning, and sand storms. It also plays a key role in several industrial processes, including ink-jet printing and electrostatic separation. Surprisingly, little is known about the underlying physics of these charging phenomena. Since thin films of water are ubiquitous, they may play a role in these charge separation processes. This talk will focus on the experimental investigation of the role of a water adlayer in interfacial charging, with relevance to meteorologically important phenomena, such as atmospheric charging due to wave actions on oceans and sand storms. An ocean wave generates thousands of bubbles, which upon bursting produce numerous large jet droplets and small film droplets that are charged. In the 1960s, Blanchard showed that the jet droplets are positively charged. However, the charge on the film droplets was not known. We designed an experiment to exclusively measure the charge on film droplets generated by bubble bursting on pure water and aqueous salt solution surfaces. We measured their charge to be negative and proposed a model where a slight excess of hydroxide ions in the interfacial water layer is responsible for generating these negatively charged droplets. The findings from this research led to a better understanding of the ionic disposition at the air-water interface. Sand particles in a wind-blown sand layer, or 'saltation' layer, become charged due to collisions, so much so, that it can cause lightning. Silica, being hydrophilic, is coated with a water layer even under low-humidity conditions. To investigate the importance of this water adlayer in charging the silica surfaces, we performed experiments to measure the charge on silica surfaces due to contact and collision processes. In case of contact charging, the maximum charge separation occurred at an optimum relative humidity. On the contrary, in collisional charging process, no humidity effect was observed. We proposed an ion transfer mechanism in case of contact charging. However, an electron transfer mechanism explained the collisional charging process. The effects of temperature, surface roughness, and chemical nature of surface were also studied for both contact and collisional charging processes.

Polyelectrolytes tethered to a free surface

NASA Astrophysics Data System (ADS)

Dubreuil, F.; Guenoun, P.

Several attempts have been already carried out in order to tether charged chains by an end at a free fluctuating surface. We review here most of these attempts and focus on how close the physics of charged brushes can be investigated by such an approach. We first describe results about films of charged-neutral diblock copolymers spread at the surface of water. Results can be mostly rationalized in terms of charged brushes although additional structurations and fluctuations of the interface can be observed. The latter deformations are also observed when adsorbed layers of charged-neutral diblock copolymers are considered. At last, we examine how free suspended films of charged-neutral diblock copolymers can be viewed as two opposing charged brushes, both in terms of thickness and pressure.

Diesel engine emissions reduction by multiple injections having increasing pressure

DOEpatents

Reitz, Rolf D.; Thiel, Matthew P.

2003-01-01

Multiple fuel charges are injected into a diesel engine combustion chamber during a combustion cycle, and each charge after the first has successively greater injection pressure (a higher injection rate) than the prior charge. This injection scheme results in reduced emissions, particularly particulate emissions, and can be implemented by modifying existing injection system hardware. Further enhancements in emissions reduction and engine performance can be obtained by using known measures in conjunction with the invention, such as Exhaust Gas Recirculation (EGR).

Depletion region surface effects in electron beam induced current measurements.

PubMed

Haney, Paul M; Yoon, Heayoung P; Gaury, Benoit; Zhitenev, Nikolai B

2016-09-07

Electron beam induced current (EBIC) is a powerful characterization technique which offers the high spatial resolution needed to study polycrystalline solar cells. Current models of EBIC assume that excitations in the p - n junction depletion region result in perfect charge collection efficiency. However we find that in CdTe and Si samples prepared by focused ion beam (FIB) milling, there is a reduced and nonuniform EBIC lineshape for excitations in the depletion region. Motivated by this, we present a model of the EBIC response for excitations in the depletion region which includes the effects of surface recombination from both charge-neutral and charged surfaces. For neutral surfaces we present a simple analytical formula which describes the numerical data well, while the charged surface response depends qualitatively on the location of the surface Fermi level relative to the bulk Fermi level. We find the experimental data on FIB-prepared Si solar cells is most consistent with a charged surface, and discuss the implications for EBIC experiments on polycrystalline materials.

Potentiometric Titrations for Measuring the Capacitance of Colloidal Photodoped ZnO Nanocrystals.

PubMed

Brozek, Carl K; Hartstein, Kimberly H; Gamelin, Daniel R

2016-08-24

Colloidal semiconductor nanocrystals offer a unique opportunity to bridge molecular and bulk semiconductor redox phenomena. Here, potentiometric titration is demonstrated as a method for quantifying the Fermi levels and charging potentials of free-standing colloidal n-type ZnO nanocrystals possessing between 0 and 20 conduction-band electrons per nanocrystal, corresponding to carrier densities between 0 and 1.2 × 10(20) cm(-3). Potentiometric titration of colloidal semiconductor nanocrystals has not been described previously, and little precedent exists for analogous potentiometric titration of any soluble reductants involving so many electrons. Linear changes in Fermi level vs charge-carrier density are observed for each ensemble of nanocrystals, with slopes that depend on the nanocrystal size. Analysis indicates that the ensemble nanocrystal capacitance is governed by classical surface electrical double layers, showing no evidence of quantum contributions. Systematic shifts in the Fermi level are also observed with specific changes in the identity of the charge-compensating countercation. As a simple and contactless alternative to more common thin-film-based voltammetric techniques, potentiometric titration offers a powerful new approach for quantifying the redox properties of colloidal semiconductor nanocrystals.

Significance of surface charge and shell material of superparamagnetic iron oxide nanoparticle (SPION) based core/shell nanoparticles on the composition of the protein corona.

PubMed

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Coullerez, Geraldine; Hofmann-Amtenbrink, Margarethe; Vries, Marcel; Motazacker, Mahdi; Rezaee, Farhad; Hofmann, Heinrich

2015-02-01

As nanoparticles (NPs) are increasingly used in many applications their safety and efficient applications in nanomedicine have become concerns. Protein coronas on nanomaterials' surfaces can influence how the cell "recognizes" nanoparticles, as well as the in vitro and in vivo NPs' behaviors. The SuperParamagnetic Iron Oxide Nanoparticle (SPION) is one of the most prominent agents because of its superparamagnetic properties, which is useful for separation applications. To mimic surface properties of different types of NPs, a core-shell SPION library was prepared by coating with different surfaces: polyvinyl alcohol polymer (PVA) (positive, neutral and negative), SiO2 (positive and negative), titanium dioxide and metal gold. The SPIONs with different surfaces were incubated at a fixed serum : nanoparticle surface ratio, magnetically trapped and washed. The tightly bound proteins were quantified and identified. The surface charge has a great impact on protein adsorption, especially on PVA and silica where proteins preferred binding to the neutral and positively charged surfaces. The importance of surface material on protein adsorption was also revealed by preferential binding on TiO2 and gold coated SPION, even negatively charged. There is no correlation between the protein net charge and the nanoparticle surface charge on protein binding, nor direct correlation between the serum proteins' concentration and the proteins detected in the coronas.

Determination of the surface charge density and temperature dependence of purple membrane by electric force microscopy.

PubMed

Du, Huiwen; Li, Denghua; Wang, Yibing; Wang, Chenxuan; Zhang, Dongdong; Yang, Yan-lian; Wang, Chen

2013-08-29

We report here the measurement of the temperature-dependent surface charge density of purple membrane (PM) by using electrostatic force microscopy (EFM). The surface charge density was measured to be 3.4 × 10(5) e/cm(2) at room temperature and reaches the minimum at around 52 °C. The initial decrease of the surface charge density could be attributed to the reduced dipole alignment because of the thermally induced protein mobility in PM. The increase of charge density at higher temperature could be ascribed to the weakened interaction between proteins and the lipids, which leads to the exposure of the charged amino acids. This work could be a benefit to the direct assessment of the structural stability and electric properties of biological membranes at the nanoscale.

Surface-Charge-Based Micro-Models--A Solid Foundation for Learning about Direct Current Circuits

ERIC Educational Resources Information Center

Hirvonen, P. E.

2007-01-01

This study explores how the use of a surface-charge-based instructional approach affects introductory university level students' understanding of direct current (dc) circuits. The introduced teaching intervention includes electrostatics, surface-charge-based micro-models that explain the existence of an electric field inside the current-carrying…

Modulating interactions between ligand-coated nanoparticles and phase-separated lipid bilayers by varying the ligand density and the surface charge.

PubMed

Chen, Xiaojie; Tieleman, D Peter; Liang, Qing

2018-02-01

The interactions between nanoparticles and lipid bilayers are critical in applications of nanoparticles in nanomedicine, cell imaging, toxicology, and elsewhere. Here, we investigate the interactions between nanoparticles coated with neutral and/or charged ligands and phase-separated lipid bilayers using coarse-grained molecular dynamics simulation. Both penetration and adsorption processes as well as the final distribution of the nanoparticles can be readily modulated by varying the ligand density and the surface charge of the nanoparticles. Completely hydrophobic (neutral) nanoparticles with larger size initially preferentially penetrate into the liquid-disordered region of the lipid bilayer and finally transfer into the liquid-ordered region; partially hydrophilic nanoparticles with low or moderate surface charge tend to either distribute in the liquid-disordered region or be adsorbed on the surface of the lipid bilayer, while strongly hydrophilic nanoparticles with high surface charge always reside on the surface of the lipid bilayer. Interactions of the nanoparticles with the lipid bilayers are affected by the surface charge of nanoparticles, hydrophobic mismatch, bending of the ligands, and the packing state of the lipids. Insight in these factors can be used to improve the efficiency of designing nanoparticles for specific applications.

Modulation of Silica Nanoparticle Uptake into Human Osteoblast Cells by Variation of the Ratio of Amino and Sulfonate Surface Groups: Effects of Serum

PubMed Central

2015-01-01

To study the importance of the surface charge for cellular uptake of silica nanoparticles (NPs), we synthesized five different single- or multifunctionalized fluorescent silica NPs (FFSNPs) by introducing various ratios of amino and sulfonate groups into their surface. The zeta potential values of these FFSNPs were customized from highly positive to highly negative, while other physicochemical properties remained almost constant. Irrespective of the original surface charge, serum proteins adsorbed onto the surface, neutralized the zeta potential values, and prevented the aggregation of the tailor-made FFSNPs. Depending on the surface charge and on the absence or presence of serum, two opposite trends were found concerning the cellular uptake of FFSNPs. In the absence of serum, positively charged NPs were more strongly accumulated by human osteoblast (HOB) cells than negatively charged NPs. In contrast, in serum-containing medium, anionic FFSNPs were internalized by HOB cells more strongly, despite the similar size and surface charge of all types of protein-covered FFSNPs. Thus, at physiological condition, when the presence of proteins is inevitable, sulfonate-functionalized silica NPs are the favorite choice to achieve a desired high rate of NP internalization. PMID:26030456

Increasing binding density of yeast cells by control of surface charge with allylamine grafting to ion modified polymer surfaces.

PubMed

Tran, Clara T H; Kondyurin, Alexey; Chrzanowski, Wojciech; Bilek, Marcela M M; McKenzie, David R

2014-10-01

Plasma immersion ion implantation (PIII) treatment of polymers creates a biointerface capable of direct covalent immobilization of biomolecules. The immobilization of protein molecules is achieved by covalent bonds formed between embedded radicals on the treated surface and amino acid side chains and cells can be immobilized through cell-wall proteins. The attachment density of negatively charged entities on a PIII treated surface is inhibited by its negative surface charge at neutral pH. To reduce the negative charge of PIII treated surfaces in phosphate buffer (pH 7.4, 11mM), we develop an effective approach of grafting allylamine monomers onto the treated surface. The results reveal reactions between allylamine and radicals on the PIII treated surface. One of these triggers polymerization, increasing the number of amine groups grafted. As a consequence, the PIII treated polystyrene surface after allylamine exposure becomes more hydrophobic and less negatively charged in phosphate buffer. Using yeast cells as an example, we have shown a significant improvement (6-15 times) of cell density immobilized on the PIII treated surface after exposure to allylamine. Copyright © 2014 Elsevier B.V. All rights reserved.

Numerical modelling of needle-grid electrodes for negative surface corona charging system

NASA Astrophysics Data System (ADS)

Zhuang, Y.; Chen, G.; Rotaru, M.

2011-08-01

Surface potential decay measurement is a simple and low cost tool to examine electrical properties of insulation materials. During the corona charging stage, a needle-grid electrodes system is often used to achieve uniform charge distribution on the surface of the sample. In this paper, a model using COMSOL Multiphysics has been developed to simulate the gas discharge. A well-known hydrodynamic drift-diffusion model was used. The model consists of a set of continuity equations accounting for the movement, generation and loss of charge carriers (electrons, positive and negative ions) coupled with Poisson's equation to take into account the effect of space and surface charges on the electric field. Four models with the grid electrode in different positions and several mesh sizes are compared with a model that only has the needle electrode. The results for impulse current and surface charge density on the sample clearly show the effect of the extra grid electrode with various positions.

Protein interactions with layers of TiO2 nanotube and nanopore arrays: Morphology and surface charge influence.

PubMed

Kulkarni, Mukta; Mazare, Anca; Park, Jung; Gongadze, Ekaterina; Killian, Manuela Sonja; Kralj, Slavko; von der Mark, Klaus; Iglič, Aleš; Schmuki, Patrik

2016-11-01

In the present work we investigate the key factors involved in the interaction of small-sized charged proteins with TiO 2 nanostructures, i.e. albumin (negatively charged), histone (positively charged). We examine anodic nanotubes with specific morphology (simultaneous control over diameter and length, e.g. diameter - 15, 50 or 100nm, length - 250nm up to 10μm) and nanopores. The nanostructures surface area has a direct influence on the amount of bound protein, nonetheless the protein physical properties as electric charge and size (in relation to nanotopography and biomaterial's electric charge) are crucial too. The highest quantity of adsorbed protein is registered for histone, for 100nm diameter nanotubes (10μm length) while higher values are registered for 15nm diameter nanotubes when normalizing protein adsorption to nanostructures' surface unit area (evaluated from dye desorption measurements) - consistent with theoretical considerations. The proteins presence on the nanostructures is evaluated by XPS and ToF-SIMS; additionally, we qualitatively assess their presence along the nanostructures length by ToF-SIMS depth profiles, with decreasing concentration towards the bottom. Surface nanostructuring of titanium biomedical devices with TiO 2 nanotubes was shown to significantly influence the adhesion, proliferation and differentiation of mesenchymal stem cells (and other cells too). A high level of control over the nanoscale topography and over the surface area of such 1D nanostructures enables a direct influence on protein adhesion. Herein, we investigate and show how the nanostructure morphology (nanotube diameter and length) influences the interactions with small-sized charged proteins, using as model proteins bovine serum albumin (negatively charged) and histone (positively charged). We show that the protein charge strongly influences their adhesion to the TiO 2 nanostructures. Protein adhesion is quantified by ELISA measurements and determination of the nanostructures' total surface area. We use a quantitative surface charge model to describe charge interactions and obtain an increased magnitude of the surface charge density at the top edges of the nanotubes. In addition, we track the proteins presence on and inside the nanostructures. We believe that these aspects are crucial for applications where the incorporation of active molecules such as proteins, drugs, growth factors, etc., into nanotubes is desired. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Surface transport processes in charged porous media

DOE PAGES

Gabitto, Jorge; Tsouris, Costas

2017-03-03

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

Dust Grain Charge above the Lunar terminator

NASA Astrophysics Data System (ADS)

Vaverka, Jakub; Richterova, Ivana; Nemecek, Zdenek; Safrankova, Jana; Pavlu, Jiri; Vysinka, Marek

Interaction of a lunar surface with the solar wind and magnetosphere leads to its charging by several processes as photoemission, a collection of primary particles, and secondary electron emission. Nevertheless, charging of the lunar surface is complicated by a shielding of solar light and solar wind ions by hills, craters, and boulders that can locally influence the surface potential. Moreover, a presence of a plasma wake can strongly affect this potential at the night side of the Moon. A typical surface potential varies from slightly positive (dayside) to negative values of the order of several hundred volts (night side). An electric field above the charged surface can lead to a levitation of dust grains as it has been observed by several spacecraft and by astronauts during Apollo missions. Although charging and transport of dust grains above the lunar surface are in the center of interest for many years, these phenomena are not still completely understood. We present calculation of an equilibrium potential of dust grains above the lunar surface. We focus on a terminator area during the Earth’s plasma sheet crossing. We use the secondary electron emission model for dust grains which takes into account an influence of the grain size, material, and surface roughness and findings from laboratory experiments with charging of lunar dust simulants by an electron beam.

Surface transport processes in charged porous media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gabitto, Jorge; Tsouris, Costas

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

Profiling Charge Complementarity and Selectivity for Binding at the Protein Surface

PubMed Central

Sulea, Traian; Purisima, Enrico O.

2003-01-01

A novel analysis and representation of the protein surface in terms of electrostatic binding complementarity and selectivity is presented. The charge optimization methodology is applied in a probe-based approach that simulates the binding process to the target protein. The molecular surface is color coded according to calculated optimal charge or according to charge selectivity, i.e., the binding cost of deviating from the optimal charge. The optimal charge profile depends on both the protein shape and charge distribution whereas the charge selectivity profile depends only on protein shape. High selectivity is concentrated in well-shaped concave pockets, whereas solvent-exposed convex regions are not charge selective. This suggests the synergy of charge and shape selectivity hot spots toward molecular selection and recognition, as well as the asymmetry of charge selectivity at the binding interface of biomolecular systems. The charge complementarity and selectivity profiles map relevant electrostatic properties in a readily interpretable way and encode information that is quite different from that visualized in the standard electrostatic potential map of unbound proteins. PMID:12719221

Deionization and desalination using electrostatic ion pumping

DOEpatents

Bourcier, William L.; Aines, Roger D.; Haslam, Jeffery J.; Schaldach, Charlene M.; O& #x27; Brien, Kevin C.; Cussler, Edward

2013-06-11

The present invention provides a new method and apparatus/system for purifying ionic solutions, such as, for example, desalinating water, using engineered charged surfaces to sorb ions from such solutions. Surface charge is applied externally, and is synchronized with oscillatory fluid movements between substantially parallel charged plates. Ions are held in place during fluid movement in one direction (because they are held in the electrical double layer), and released for transport during fluid movement in the opposite direction by removing the applied electric field. In this way the ions, such as salt, are "ratcheted" across the charged surface from the feed side to the concentrate side. The process itself is very simple and involves only pumps, charged surfaces, and manifolds for fluid collection.

Deionization and desalination using electrostatic ion pumping

DOEpatents

Bourcier, William L [Livermore, CA; Aines, Roger D [Livermore, CA; Haslam, Jeffery J [Livermore, CA; Schaldach, Charlene M [Pleasanton, CA; O'Brien, Kevin C [San Ramon, CA; Cussler, Edward [Edina, MN

2011-07-19

The present invention provides a new method and apparatus/system for purifying ionic solutions, such as, for example, desalinating water, using engineered charged surfaces to sorb ions from such solutions. Surface charge is applied externally, and is synchronized with oscillatory fluid movements between substantially parallel charged plates. Ions are held in place during fluid movement in one direction (because they are held in the electrical double layer), and released for transport during fluid movement in the opposite direction by removing the applied electric field. In this way the ions, such as salt, are "ratcheted" across the charged surface from the feed side to the concentrate side. The process itself is very simple and involves only pumps, charged surfaces, and manifolds for fluid collection.

A switchable polymer layer: Chain folding in end-charged polymer brushes

NASA Astrophysics Data System (ADS)

Heine, David; Wu, David T.

2001-03-01

We use a self-consistent field approximation to model the configurations of end-charged homopolymer and block copolymer brushes in response to an external electric field due to charges on the grafting surface. By varying the charge density on the grafting surface, we can cause the chains either to extend outward, greatly increasing the brush height, or to loop back to the grafting surface. We show that such a copolymer brush can present one block at the exposed surface in the extended state and present the other block in the retracted state. This occurs for both a solvated brush and a dry brush. We also compare these results to those of a modified Alexander-de Gennes model for the end-charged homopolymer brush.

Theoretical study of the two-dimensional electron mobility in strained III-nitride heterostructures

NASA Astrophysics Data System (ADS)

Yu, Tsung-Hsing; Brennan, Kevin F.

2001-04-01

We present calculations of the two-dimensional (2D) electron mobility in III-nitride heterojunction structures in the presence of spontaneous and piezoelectrically induced polarization effects. The calculations are made using a self-consistent solution of the Schrödinger, Poisson, charge and potential balance equations. It is found that the polarization fields act to significantly increase the 2D sheet charge concentration while reducing the mobility. The mobility reduction results from the enhanced band bending and subsequent attraction of the electrons to the heterointerface where they experience increased surface roughness scattering. Good agreement is obtained between the theoretical calculations and experimental measurements over the full temperature range examined. Comparison of the mobility in InGaN/GaN to AlGaN/GaN heterostructures is made. It is found that the mobility is significantly higher in the InGaN/GaN structure than in the AlGaN/GaN structure.

Kinetics of optically excited charge carriers at the GaN surface: Influence of catalytic Pt nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winnerl, Andrea, E-mail: andrea.winnerl@wsi.tum.de; Pereira, Rui N.; Stutzmann, Martin

2015-10-21

In this work, we use GaN with different deposited Pt nanostructures as a controllable model system to investigate the kinetics of photo-generated charge carriers in hybrid photocatalysts. We combine conductance and contact potential difference measurements to investigate the influence of Pt on the processes involved in the capture and decay of photo-generated charge carriers at and close to the GaN surface. We found that in the presence of Pt nanostructures the photo-excitation processes are similar to those found in Pt free GaN. However, in GaN with Pt nanostructures, photo-generated holes are preferentially trapped in surface states of the GaN coveredmore » with Pt and/or in electronic states of the Pt and lead to an accumulation of positive charge there, whereas negative charge is accumulated in localized states in a shallow defect band of the GaN covered with Pt. This preferential accumulation of photo-generated electrons close to the surface is responsible for a dramatic acceleration of the turn-off charge transfer kinetics and a stronger dependence of the surface photovoltage on light intensity when compared to a Pt free GaN surface. Our study shows that in hybrid photocatalysts, the metal nanostructures induce a spatially inhomogeneous surface band bending of the semiconductor that promotes a lateral drift of photogenerated charges towards the catalytic nanostructures.« less

Mediating electrostatic binding of 1-butyl-3-methylimidazolium chloride to enzyme surfaces improves conformational stability.

PubMed

Nordwald, Erik M; Kaar, Joel L

2013-08-01

We have recently developed a general approach to improve the utility of enzymes in ionic liquids (ILs) via tuning of the ratio of enzyme-containing positive to negative surface charges. In this work, the impact of enzyme surface charge ratio on the biophysical interaction of 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]) with chymotrypsin and lipase was investigated to understand this approach at the molecular level. Results of fluorescence quenching assays indicated that the extent of binding of the [BMIM] cation decreased (7- and 3.5-fold for chymotrypsin and lipase, respectively) as a function of increasing ratio of positive to negative surface charges. Conformational stability assays further showed a close correlation between thermodynamic stabilization and enzyme surface charge ratio as well as [BMIM] binding. As evidence of this correlation, succinylation and acetylation resulted in the stabilization of chymotrypsin in 10% (v/v) [BMIM][Cl] by 17.0 and 6.6 kJ/mol, respectively, while cationization destabilized chymotrypsin by 3.6 kJ/mol. Combined, these results indicate that altering the surface charge ratio mediates the organization of IL molecules, namely, [BMIM] and [Cl], around the enzymes. Preferential exclusion of [Cl], in particular, via lowering of the ratio of positive to negative surface charges, correlated with increased enzyme stability. Accordingly, these results more broadly provide insight into the mechanism of stabilization in ILs via charge modification.

Effect of Atomic Oxygen Exposure on Surface Resistivity Change of Spacecraft Insulator Material

NASA Astrophysics Data System (ADS)

Mundari, Noor Danish Ahrar; Khan, Arifur Rahman; Chiga, Masaru; Okumura, Teppei; Masui, Hirokazu; Iwata, Minoru; Toyoda, Kazuhiro; Cho, Mengu

Spacecraft surface charging can lead to arcing and a loss of electricity generation capability in solar panels or even loss of a satellite. The charging problem may be further aggravated by atomic oxygen (AO) exposure in Low Earth orbits, which modifies the surface of materials like polyimide, Teflon, anti-reflective coatings, cover glass etc, used on satellite surfaces, affecting materials properties, such as resistivity, secondary electron emissivity and photo emission, which govern the charging behavior. These properties are crucial input parameters for spacecraft charging analysis. To study the AO exposure effect on charging governing properties, an atomic oxygen exposure facility based on laser detonation of oxygen was built. The facility produces AO with a peak velocity value around 10-12km/s and a higher flux than that existing in orbit. After exposing the polyimide test material to the equivalent of 10 years of AO fluence at an altitude of 700-800 km, surface charging properties like surface resistivity and volume resistivity were measured. The measurement was performed in a vacuum using the charge storage decay method at room temperature, which is considered the most appropriate for measuring resistivity for space applications. The results show that the surface resistivity increases and the volume resistivity remains almost the same for the AO exposure fluence of 5.4×1018 atoms cm-2.

Atomistic Molecular Dynamics Simulations of Charged Latex Particle Surfaces in Aqueous Solution.

PubMed

Li, Zifeng; Van Dyk, Antony K; Fitzwater, Susan J; Fichthorn, Kristen A; Milner, Scott T

2016-01-19

Charged particles in aqueous suspension form an electrical double layer at their surfaces, which plays a key role in suspension properties. For example, binder particles in latex paint remain suspended in the can because of repulsive forces between overlapping double layers. Existing models of the double layer assume sharp interfaces bearing fixed uniform charge, and so cannot describe aqueous binder particle surfaces, which are soft and diffuse, and bear mobile charge from ionic surfactants as well as grafted multivalent oligomers. To treat this industrially important system, we use atomistic molecular dynamics simulations to investigate a structurally realistic model of commercial binder particle surfaces, informed by extensive characterization of particle synthesis and surface properties. We determine the interfacial profiles of polymer, water, bound and free ions, from which the charge density and electrostatic potential can be calculated. We extend the traditional definitions of the inner and outer Helmholtz planes to our diffuse interfaces. Beyond the Stern layer, the simulated electrostatic potential is well described by the Poisson-Boltzmann equation. The potential at the outer Helmholtz plane compares well to the experimental zeta potential. We compare particle surfaces bearing two types of charge groups, ionic surfactant and multivalent oligomers, with and without added salt. Although the bare charge density of a surface bearing multivalent oligomers is much higher than that of a surfactant-bearing surface at realistic coverage, greater counterion condensation leads to similar zeta potentials for the two systems.

Reduction Behavior of Assmang and Comilog ore in the SiMn Process

NASA Astrophysics Data System (ADS)

Kim, Pyunghwa Peace; Holtan, Joakim; Tangstad, Merete

The reduction behavior of raw materials from Assmang and Comilog based charges were experimentally investigated with CO gas up to 1600 °C. Quartz, HC FeMn slag or limestone were added to Assmang or Comilog according to the SiMn production charge, and mass loss results were obtained by using a TGA furnace. The results showed that particle size, type of manganese ore and mixture have close relationship to the reduction behavior of raw materials during MnO and SiO2 reduction. The influence of particle size to mass loss was apparent when Assmang or Comilog was mixed with only coke (FeMn) while it became insignificant when quartz and HC FeMn slag (SiMn) were added. This implied that quartz and HC FeMn slag had favored the incipient slag formation regardless of particle size. This explained the similar mass loss tendencies of SiMn charge samples between 1200-1500 °C, contrary to FeMn charge samples where different particle sizes showed significant difference in mass loss. Also, while FeMn charge samples showed progressive mass loss, SiMn charge samples showed diminutive mass loss until 1500 °C. However, rapid mass losses were observed with SiMn charge samples in this study above 1500 °C, and they have occurred at different temperatures. This implied rapid reduction of MnO and SiO2 and the type of ore and addition of HC FeMn slag have significant influence determining these temperatures. The temperatures observed for the rapid mass loss were approximately 1503 °C (Quartz and HC FeMn slag addition in Assmang), 1543 °C (Quartz addition in Assmang) and 1580-1587 °C (Quartz and limestone addition in Comilog), respectively. These temperatures also showed indications of possible SiMn production at process temperatures lower than 1550 °C.

Final case for a stainless steel diagnostic first wall on ITER

NASA Astrophysics Data System (ADS)

Pitts, R. A.; Bazylev, B.; Linke, J.; Landman, I.; Lehnen, M.; Loesser, D.; Loewenhoff, Th.; Merola, M.; Roccella, R.; Saibene, G.; Smith, M.; Udintsev, V. S.

2015-08-01

In 2010 the ITER Organization (IO) proposed to eliminate the beryllium armour on the plasma-facing surface of the diagnostic port plugs and instead to use bare stainless steel (SS), simplifying the design and providing significant cost reduction. Transport simulations at the IO confirmed that charge-exchange sputtering of the SS surfaces would not affect burning plasma operation through core impurity contamination, but a second key issue is the potential melt damage/material loss inflicted by the intense photon radiation flashes expected at the thermal quench of disruptions mitigated by massive gas injection. This paper addresses this second issue through a combination of ITER relevant experimental heat load tests and qualitative theoretical arguments of melt layer stability. It demonstrates that SS can be employed as material for the port plug plasma-facing surface and this has now been adopted into the ITER baseline.

Label-free CMOS bio sensor with on-chip noise reduction scheme for real-time quantitative monitoring of biomolecules.

PubMed

Seong-Jin Kim; Euisik Yoon

2012-06-01

We present a label-free CMOS field-effect transistor sensing array to detect the surface potential change affected by the negative charge in DNA molecules for real-time monitoring and quantification. The proposed CMOS bio sensor includes a new sensing pixel architecture implemented with correlated double sampling for reducing offset fixed pattern noise and 1/f noise of the sensing devices. We incorporated non-surface binding detection which allows real-time continuous monitoring of DNA concentrations without immobilizing them on the sensing surface. Various concentrations of 19-bp oligonucleotides solution can be discriminated using the prototype device fabricated in 1- μm double-poly double-metal standard CMOS process. The detection limit was measured as 1.1 ng/μl with a dynamic range of 40 dB and the transient response time was measured less than 20 seconds.

Host-guest chemistry of dendrimer-drug complexes. 2. Effects of molecular properties of guests and surface functionalities of dendrimers.

PubMed

Hu, Jingjing; Cheng, Yiyun; Wu, Qinglin; Zhao, Libo; Xu, Tongwen

2009-08-06

The host-guest chemistry of dendrimer-drug complexes is investigated by NMR techniques, including (1)H NMR and 2D-NOESY studies. The effects of molecular properties of drug molecules (protonation ability and spatial steric hindrance of charged groups) and surface functionalities of dendrimers (positively charged amine groups and negatively charged carboxylate groups) on the host-guest interactions are discussed. Different interaction mechanisms between dendrimers and drug molecules are proposed on the basis of NMR results. Primary amine- and secondary amine-containing drugs preferentially bind to negatively charged dendrimers by strong electrostatic interactions, whereas tertiary amine and quaternary ammonium-containing drugs have weak binding ability with dendrimers due to relatively low protonation ability of the tertiary amine group and serious steric hindrance of the quaternary ammonium group. Positively charged drugs locate only on the surface of negatively charged dendrimers, whereas negatively charged drugs locate both on the surface and in the interior cavities of positively charged dendrimers. The host-guest chemistry of dendrimer-drug complexes is promising for the development of new drug delivery systems.

Effect of surface charge alteration on stability of L-asparaginase II from Escherichia sp.

PubMed

Vidya, Jalaja; Ushasree, Mrudula Vasudevan; Pandey, Ashok

2014-03-05

Escherichia coli L-asparaginases have great significance in the treatment of leukemia. Consequently, there is considerable interest in engineering this enzyme for improving its stability. In this work, the effect of surface charge on the stability of the enzyme l-asparaginase II was studied by site-directed mutagenesis of the cloned ansB gene from Escherichia sp. Replacement of two positively charged residues (K139 and K207) on the surface loops with neutral and reverse charges resulted in altered thermo stability in designed variants. Neutral charge substitutions (K139A and K207A) retained greater tolerance and stability followed by negative charge substitutions (K139D and K207D) compared to control mutant K139R and wild enzyme. From the results, it was concluded that the optimization of surface charge contributed much to the thermal properties of proteins without affecting the structure. Copyright © 2013 Elsevier Inc. All rights reserved.

Analysis of microscopic parameters of surface charging in polymer caused by defocused electron beam irradiation.

PubMed

Liu, Jing; Zhang, Hai-Bo

2014-12-01

The relationship between microscopic parameters and polymer charging caused by defocused electron beam irradiation is investigated using a dynamic scattering-transport model. The dynamic charging process of an irradiated polymer using a defocused 30 keV electron beam is conducted. In this study, the space charge distribution with a 30 keV non-penetrating e-beam is negative and supported by some existing experimental data. The internal potential is negative, but relatively high near the surface, and it decreases to a maximum negative value at z=6 μm and finally tend to 0 at the bottom of film. The leakage current and the surface potential behave similarly, and the secondary electron and leakage currents follow the charging equilibrium condition. The surface potential decreases with increasing beam current density, trap concentration, capture cross section, film thickness and electron-hole recombination rate, but with decreasing electron mobility and electron energy. The total charge density increases with increasing beam current density, trap concentration, capture cross section, film thickness and electron-hole recombination rate, but with decreasing electron mobility and electron energy. This study shows a comprehensive analysis of microscopic factors of surface charging characteristics in an electron-based surface microscopy and analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

The role of surface charge density in cationic liposome-promoted dendritic cell maturation and vaccine-induced immune responses

NASA Astrophysics Data System (ADS)

Ma, Yifan; Zhuang, Yan; Xie, Xiaofang; Wang, Ce; Wang, Fei; Zhou, Dongmei; Zeng, Jianqiang; Cai, Lintao

2011-05-01

Cationic liposomes have emerged as a novel adjuvant and antigen delivery system to enhance vaccine efficacy. However, the role of surface charge density in cationic liposome-regulated immune responses has not yet been elucidated. In the present study, we prepared a series of DOTAP/DOPC cationic liposomes with different surface densities by incorporating varying amounts of DOPC (a neutral lipid) into DOTAP (a cationic lipid). The results showed that DOTAP/DOPC cationic liposome-regulated immune responses relied on the surface charge density, and might occur through ROS signaling. The liposomes with a relatively high charge density, such as DOTAP/DOPC 5 : 0 and 4 : 1 liposomes, potently enhanced dendritic cell maturation, ROS generaion, antigen uptake, as well as the production of OVA-specific IgG2a and IFN-γ. In contrast, low-charge liposomes, such as DOTAP/DOPC 1 : 4 liposome, failed to promote immune responses even at high concentrations, confirming that the immunoregulatory effect of cationic liposomes is mostly attributable to their surface charge density. Moreover, the DOTAP/DOPC 1 : 4 liposome suppressed anti-OVA antibody responses in vivo. Overall, maintaining an appropriate surface charge is crucial for optimizing the adjuvant effect of cationic liposomes and enhancing the efficacy of liposome-based vaccines.

Harvesting visible light with MoO3 nanorods modified by Fe(iii) nanoclusters for effective photocatalytic degradation of organic pollutants.

PubMed

Alam, U; Kumar, S; Bahnemann, D; Koch, J; Tegenkamp, C; Muneer, M

2018-02-07

The photocatalytic performance of MoO 3 is limited due to its weak visible light absorption ability and quick recombination of charge carriers. In the present work, we report the facile synthesis of Fe(iii)-grafted MoO 3 nanorods using a hydrothermal method followed by an impregnation technique with the aim of enhancing the light harvesting ability and photocatalytic efficiency of MoO 3 . The prepared samples were characterized through the standard analytical techniques of XRD, SEM-EDS, TEM, XPS, UV-Vis-DRS, FT-IR, TG-DTA and PL spectrophotometry. XPS and TEM analyses reveal that Fe(iii) ions are successfully grafted onto the surface of the MoO 3 nanorod with intimate interfacial contact. The photocatalytic performances of the prepared samples were investigated by studying the degradation of methylene blue (MB), rhodamine B (RhB) and 4-nitrophenol (4-NP) under visible light irradiation. The surface-modified MoO 3 with Fe(iii) ions showed excellent photocatalytic activity towards the degradation of the above-mentioned pollutants, where Fe(iii) ions act as effective cocatalytic sites to produce hydroxyl radicals through multi-electron reduction of oxygen molecules. The improved photocatalytic activity could be ascribed to the effective separation of charge carriers and efficient production of hydroxyl radicals via the rapid capture of electrons by Fe(iii) through a well-known photoinduced interfacial charge transfer mechanism. Based on scavenger analysis study, a mechanism for the enhanced photocatalytic activity has been discussed and proposed. The concept of surface grafting onto large bandgap semiconductors with ubiquitous elements opens up a new avenue for the development of visible-light-responsive photocatalysts with excellent photocatalytic activity.

Silica nanogelling of environment-responsive PEGylated polyplexes for enhanced stability and intracellular delivery of siRNA.

PubMed

Gouda, Noha; Miyata, Kanjiro; Christie, R James; Suma, Tomoya; Kishimura, Akihiro; Fukushima, Shigeto; Nomoto, Takahiro; Liu, Xueying; Nishiyama, Nobuhiro; Kataoka, Kazunori

2013-01-01

In this study, poly(ethylene glycol) (PEG)-block-polycation/siRNA complexes (PEGylated polyplexes) were wrapped with a hydrated silica, termed "silica nanogelling", in order to enhance their stability and functionality. Silica nanogelling was achieved by polycondensation of soluble silicates onto the surface of PEGylated polyplexes comprising a disulfide cross-linked core. Formation of silica nanogel layer on the PEGylated cross-linked polyplexes was confirmed by particle size increase, surface charge reduction, and elemental analysis of transmission electron micrographs. Silica nanogelling substantially improved polyplex stability against counter polyanion-induced dissociation under non-reductive condition, without compromising the reductive environment-responsive siRNA release triggered by disulfide cleavage. Silica nanogelling significantly enhanced the sequence-specific gene silencing activity of the polyplexes in HeLa cells without associated cytotoxicity, probably due lower endosomal entrapment (or lysosomal degradation) of delivered siRNA. The lower endosomal entrapment of the silica nanogel system could be explained by an accelerated endosomal escape triggered by deprotonated silanol groups in the silica (the proton sponge hypothesis) and/or a modulated intracellular trafficking, possibly via macropinocytosis, as evidenced by the cellular uptake inhibition assay. Henceforth, silica nanogelling of PEGylated siRNA polyplexes is a promising strategy for preparation of stable and functional siRNA delivery vehicles. Copyright © 2012 Elsevier Ltd. All rights reserved.

Surface decoration through electrostatic interaction leading to enhanced reactivity: Low temperature synthesis of nanostructured chromium borides (CrB and CrB{sub 2})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Menaka,; Kumar, Bharat; Kumar, Sandeep

The present study describes a novel low temperature route at ambient pressure for the synthesis of nanocrystalline chromium borides (CrB and CrB{sub 2}) without using any flux or additives. The favorable and intimate mixing of nanoparticles of chromium acetate (Cr source) and boron forms an active chromium–boron precursor which decomposes at much lower temperature (400 °C) to form CrB (which is ∼1000 °C less than the known ambient pressure synthesis). The chromium acetate nanoparticles (∼5 nm) decorate the larger boron particles (150–200 nm) due to electrostatic interactions resulting from opposing surface charges of boron (zeta potential:+48.101 mV) and chromium acetatemore » (zeta potential:−4.021 mV) in ethanolic medium and is evident in the TEM micrographs. The above method leads to the formation of pure CrB film like structure at 400 °C and nanospheres (40–60 nm) at 600 °C. Also, chromium diboride (CrB{sub 2}) nanoparticles (25 nm) could be obtained at 1000 °C. - Graphical abstract: Variation of surface charge of reactants, precursor and the products, chromium borides (CrB and CrB{sub 2}). Highlights: ► Novel borothermal reduction process for synthesis of chromium boride. ► Significant lowering of reaction temperature to obtain nanocrystalline chromium boride. ► Enhanced reactivity due to appropriate surface interactions.« less

Sodium dodecyl sulfate-ethoxylated polyethylenimine adsorption at the air-water interface: how the nature of ethoxylation affects the pattern of adsorption.

PubMed

Batchelor, Stephen N; Tucker, Ian; Petkov, Jordan T; Penfold, Jeffrey; Thomas, Robert K

2014-08-19

The strong interaction between ionic surfactants and polyelectrolytes of opposite charge results in enhanced surface adsorption at the air-water interface down to low surfactant concentrations and in some cases in the formation of ordered surface structures. A notable example which exhibits such properties is the mixture of polyethylenimine, PEI, and sodium dodecyl sulfate, SDS. However, the electrostatic interaction, around charge neutralization, between the surfactant and polymer often results in precipitation or coacervation. This can be mitigated for PEI-surfactant mixtures by ethoxylation of the PEI, but this can also result in a weaker surface interaction and a significant reduction in the adsorption. It is shown here that by localizing the ethoxylation of the PEI into discrete regions of the polymer precipitation upon the addition of SDS is suppressed, the strong surface interaction and enhanced adsorption of the polymer-surfactant mixture is retained. The adsorption of SDS in the presence of ethoxylated PEI is greatly enhanced at low SDS concentrations compared to the adsorption for pure SDS. The adsorption is equally pronounced at pH 7 and 10 and is largely independent of the degree of ethoxylation. Surface ordering, more than monolayer adsorption, is observed over a relatively narrow range of SDS concentrations and is most pronounced at pH 10 and for the polymers with the lower degree of ethoxylation. The results show that ethoxylated PEI's reported here provide a suitable route to enhanced surfactant adsorption while retaining favorable solution properties in which precipitation effects are minimized.

Tuning spontaneous polarization to alter water oxidation/reduction activities of LiNbO3

NASA Astrophysics Data System (ADS)

Fu, Hongwei; Song, Yan; Wu, Yangqing; Huang, Huiting; Fan, Guozheng; Xu, Jun; Li, Zhaosheng; Zou, Zhigang

2018-02-01

Here, we investigated the effects of spontaneous polarization on photoreactivities by using a ferroelectric material n-type congruent LiNbO3 single crystal as a model. It was found that c+ LiNbO3 was superior to c- LiNbO3 in photocatalytic water reduction, while c- LiNbO3 exhibited better performances for photoelectrochemical water oxidation than c+ LiNbO3. Using Kelvin probe force microscopy and open circuit potential methods, we observed that c- LiNbO3 generated a higher photovoltage and had a slower charge-recombination rate than c+ LiNbO3. The results of electrochemical impedance spectroscopy measurements indicated that c- LiNbO3 may favor the hole transport from the bulk to the surface compared with c+ LiNbO3, leading to the anisotropic performances of c+ and c- LiNbO3 in water oxidation/reduction. Therefore, tuning the direction of the polarization may be a strategy to dramatically prompt the photoreactivities of water oxidation or reduction.

Redox-induced surface stress of polypyrrole-based actuators.

PubMed

Tabard-Cossa, Vincent; Godin, Michel; Grütter, Peter; Burgess, Ian; Lennox, R B

2005-09-22

We measure the surface stress induced by electrochemical transformations of a thin conducting polymer film. One side of a micromechanical cantilever-based sensor is covered with an electropolymerized dodecyl benzenesulfonate-doped polypyrrole (PPyDBS) film. The microcantilever serves as both the working electrode (in a conventional three-electrode cell configuration) and as the mechanical transducer for simultaneous, in situ, and real-time measurements of the current and interfacial stress changes. A compressive change in surface stress of about -2 N/m is observed when the conducting polymer is electrochemically switched between its oxidized (PPy+) and neutral (PPy0) state by cyclic voltammetry. The surface stress sensor's response during the anomalous first reductive scan is examined. The effect of long-term cycling on the mechanical transformation ability of PPy(DBS) films in both surfactant and halide-based electrolytes is also discussed. We have identified two main competing origins of surface stress acting on the PPy(DBS)/ gold-coated microcantilever: one purely mechanical due to the volume change of the conducting polymer, and a second charge-induced, owing to the interaction of anions of the supporting electrolyte with the gold surface.

Charge reversal at a planar boundary between two dielectrics.

PubMed

Wang, Zhi-Yong

2016-01-01

Despite the ubiquitous character and relevance of the electric double layer in the entire realm of interface and colloid science, very little is known of the effect that surface heterogeneity exerts on the underlying mechanisms of ion adsorption. Herein, computer simulations offer a perspective that, in sharp contrast to the homogeneously charged surface, discrete groups promote multivalent counterion binding, leading to charge reversal but possibly having not a sign change of the electrophoretic mobility. Counterintuitively, the introduction of dielectric images yields a significantly greater accumulation of counterions, which further facilitates the magnitude of charge reversal. The reported results are very sensitive to both the degree of ion hydration and the representation of surface charges. Our findings shed light on the mechanism for charge reversal over a broad range of coupling regimes operating the adsorption of counterions through surface group bridging attraction with their own images and provide opportunities for experimental studies and theoretical development.

Charge reversal at a planar boundary between two dielectrics

NASA Astrophysics Data System (ADS)

Wang, Zhi-Yong

2016-01-01

Despite the ubiquitous character and relevance of the electric double layer in the entire realm of interface and colloid science, very little is known of the effect that surface heterogeneity exerts on the underlying mechanisms of ion adsorption. Herein, computer simulations offer a perspective that, in sharp contrast to the homogeneously charged surface, discrete groups promote multivalent counterion binding, leading to charge reversal but possibly having not a sign change of the electrophoretic mobility. Counterintuitively, the introduction of dielectric images yields a significantly greater accumulation of counterions, which further facilitates the magnitude of charge reversal. The reported results are very sensitive to both the degree of ion hydration and the representation of surface charges. Our findings shed light on the mechanism for charge reversal over a broad range of coupling regimes operating the adsorption of counterions through surface group bridging attraction with their own images and provide opportunities for experimental studies and theoretical development.

Electrostatic thin film chemical and biological sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prelas, Mark A.; Ghosh, Tushar K.; Tompson, Jr., Robert V.

A chemical and biological agent sensor includes an electrostatic thin film supported by a substrate. The film includes an electrostatic charged surface to attract predetermined biological and chemical agents of interest. A charge collector associated with said electrostatic thin film collects charge associated with surface defects in the electrostatic film induced by the predetermined biological and chemical agents of interest. A preferred sensing system includes a charge based deep level transient spectroscopy system to read out charges from the film and match responses to data sets regarding the agents of interest. A method for sensing biological and chemical agents includesmore » providing a thin sensing film having a predetermined electrostatic charge. The film is exposed to an environment suspected of containing the biological and chemical agents. Quantum surface effects on the film are measured. Biological and/or chemical agents can be detected, identified and quantified based on the measured quantum surface effects.« less

Biochemical Study of Anti-Inflammatory Proteins vCCI and vMIP-II

DTIC Science & Technology

2014-07-17

protein ), where we showed that vCCI is able to bind so many different chemokines due to its general negatively charged surface , allowing it to bind...sample of these competition curves. Our conclusion from the data in Table 1 and Figure 1 is that the negatively charged surface of vCCI allows it to...Similar to our mutagenesis results, the overall data indicate that vCCI uses a negatively charged surface to bind positive charges on the chemokine

SPM observation of nano-dots induced by slow highly charged ions

NASA Astrophysics Data System (ADS)

Nakamura, Nobuyuki; Terada, Masashi; Nakai, Yoichi; Kanai, Yasuyuki; Ohtani, Shunsuke; Komaki, Ken-ichiro; Yamazaki, Yasunori

2005-05-01

We have observed nano-dots on a highly oriented pyrolytic graphite (HOPG) surface produced by highly charged ion impacts with a scanning probe microscope. In order to clarify the role of potential and kinetic energies in surface modification, we have measured the kinetic energy and incident ion charge dependences of the dot size. The results showed that the potential energy or the incident ion charge has strong influence on the surface modification rather than the kinetic energy.

Reduction of bacterial surface contamination in the hospital environment by application of a new product with persistent effect.

PubMed

Hedin, G; Rynbäck, J; Loré, B

2010-06-01

The benefit of routine surface disinfection in hospitals has been discussed. In this study we have investigated a new product, Appeartex. After application on surfaces a remnant effect is achieved due to the positive charge of the active molecule. We studied the persistent effect of Appeartex one day after application in both an experimental study in the laboratory and a field study in a hospital ward. Surfaces of bedside tables were investigated. In the experimental study, large inocula of >or=10(6)cfu of S. aureus or enterococci were inoculated on to well-defined areas which had been treated/not treated with Appeartex. One hour later, samples were taken with a swab rinse technique. A reduction in the number of viable bacteria in the magnitude 10-10(3) cfu was seen due to the effect of Appeartex. In the field study the effect on naturally occurring low level contamination was studied. Defined surfaces on bedside tables used by patients were treated/not treated with Appeartex. One day later, samples were taken with contact agar plates and with a new swab method using two sequential nylon flocked swabs. Significantly fewer bacteria were found on Appeartex-treated surfaces compared with untreated surfaces. The median counts on Appeartex-treated surfaces were 10 cfu/50 cm(2), and on untreated surfaces 20 cfu/50 cm(2). There was no significant difference in the number of bacteria found by culture of samples taken with the contact agar method compared with samples taken using the nylon flocked swab method. (c) 2010 The Hospital Infection Society. Published by Elsevier Ltd. All rights reserved.

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

PubMed

Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

2015-01-01

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electrostatic dust transport on the surfaces of airless bodies

NASA Astrophysics Data System (ADS)

Wang, X.; Schwan, J.; Hsu, H. W.; Horanyi, M.

2015-12-01

The surfaces of airless bodies are charged due to the exposure to solar wind plasma and UV radiation. Dust particles on the regolith of these surfaces can become charged, and may move and even get lofted due to electrostatic force. Electrostatic dust transport has been a long-standing problem that may be related to many observed phenomena on the surfaces of airless planetary bodies, including the lunar horizon glow, the dust ponds on asteroid Eros, the spokes in Saturn's rings, and more recently, the collection of dust particles ejected off Comet 67P, observed by Rosetta. In order to resolve these puzzles, a handful of laboratory experiments have been performed in the past and demonstrated that dust indeed moves and lifts from surfaces exposed to plasma. However, the exact mechanisms for the mobilization of dust particles still remain a mystery. Current charging models, including the so-called "shared charge model" and the charge fluctuation theory, will be discussed. It is found that neither of these models can explain the results from either laboratory experiments or in-situ observations. Recently, single dust trajectories were captured with our new dust experiments, enabling novel micro-scale investigations. The particles' initial launch speeds and size distributions are analyzed, and a new so-called "patched charge model" is proposed to explain our findings. We identify the role of plasma micro-cavities that are formed in-between neighboring dust particles. The emitted secondary or photo- electrons are proposed to be absorbed inside the micro-cavities, resulting in significant charge accumulation on the exposed patches of the surfaces of neighboring particles. The resulting enhanced Coulomb force (repulsion) between particles is likely the dominant force to mobilize and lift them off the surface. The role of other properties, including surface morphology, cohesion and photoelectron charging, will also be discussed.

Loading capacity and interaction of DNA binding on catanionic vesicles with different cationic surfactants.

PubMed

Xu, Lu; Chen, Jingfei; Feng, Lei; Dong, Shuli; Hao, Jingcheng

2014-12-07

Cationic and anionic (catanionic) vesicles were constructed from the mixtures of sodium laurate (SL) and alkyltrimethylammonium bromide (CnTAB, n = 12, 14, and 16) and were used to control the loading capacity of DNA. The binding saturation point (BSP) of DNA to catanionic vesicles increases with the chain length of cationic surfactants, which is at 1.0, 1.3 and 1.5 for CnTAB with n = 12, 14, and 16, respectively. Our measurements showed that the loading capacity and affinity of DNA can be controlled by catanionic vesicles. It increases with the chain length of cationic surfactants. Because of a large reduction in surface charge density, catanionic vesicles are prone to undergo re-aggregation or fusion with the addition of DNA. DNA molecules can still maintain original coil state during the interaction with catanionic CnTAL vesicles. (1)H NMR data reveals that the obvious dissociation of anionic ions, L(-), from catanionic C14TAL vesicles is due to the interaction with DNA; however, this phenomenon cannot be observed in C12TAB-SL vesicles. Agarose gel electrophoresis (AGE) results demonstrate that the electrostatic interaction between the two oppositely charged cationic and anionic surfactants is stronger than that between DNA and cationic surfactant, CnTAB (n = 12, 14, and 16). Not only is the dissociation of L(-) simply determined by the charge competition, but it also depends largely on the variations in the surface charge density as well as the cationic and anionic surfactant competing ability in geometry configuration of catanionic vesicles. The complicated interaction between DNA and catanionic vesicles induces the deformation of cationic vesicles. Our results should provide clear guidance for choosing more proper vectors for DNA delivery and gene therapy in cell experiments.

Influence of charge and flexibility on smectic phase formation in filamentous virus suspensions

NASA Astrophysics Data System (ADS)

Purdy, Kirstin R.; Fraden, Seth

2007-07-01

We present experimental measurements of the cholesteric-smectic phase transition of suspensions of charged semiflexible rods as a function of rod flexibility and surface charge. The rod particles consist of the bacteriophage M13 and closely related mutants, which are structurally identical to M13, but vary either in contour length and therefore ratio of persistence length to contour length, or surface charge. Surface charge is altered in two ways; by changing solution pH and by comparing M13 with fd virus, a virus which differs from M13 only by the substitution of a single charged amino acid for a neutral one per viral coat protein. Phase diagrams are measured as a function of particle length, particle charge, and ionic strength. The experimental results are compared with existing theoretical predictions for the phase behavior of flexible rods and charged rods.

Influence of radioactivity on surface charging and aggregation kinetics of particles in the atmosphere.

PubMed

Kim, Yong-Ha; Yiacoumi, Sotira; Lee, Ida; McFarlane, Joanna; Tsouris, Costas

2014-01-01

Radioactivity can influence surface interactions, but its effects on particle aggregation kinetics have not been included in transport modeling of radioactive particles. In this research, experimental and theoretical studies have been performed to investigate the influence of radioactivity on surface charging and aggregation kinetics of radioactive particles in the atmosphere. Radioactivity-induced charging mechanisms have been investigated at the microscopic level, and heterogeneous surface potential caused by radioactivity is reported. The radioactivity-induced surface charging is highly influenced by several parameters, such as rate and type of radioactive decay. A population balance model, including interparticle forces, has been employed to study the effects of radioactivity on particle aggregation kinetics in air. It has been found that radioactivity can hinder aggregation of particles because of similar surface charging caused by the decay process. Experimental and theoretical studies provide useful insights into the understanding of transport characteristics of radioactive particles emitted from severe nuclear events, such as the recent accident of Fukushima or deliberate explosions of radiological devices.

Lewis Base Passivation of Hybrid Halide Perovskites Slows Electron-Hole Recombination: Time-Domain Ab Initio Analysis.

PubMed

Liu, Lihong; Fang, Wei-Hai; Long, Run; Prezhdo, Oleg V

2018-03-01

Nonradiative electron-hole recombination plays a key role in determining photon conversion efficiencies in solar cells. Experiments demonstrate significant reduction in the recombination rate upon passivation of methylammonium lead iodide perovskite with Lewis base molecules. Using nonadiabatic molecular dynamics combined with time-domain density functional theory, we find that the nonradiative charge recombination is decelerated by an order of magnitude upon adsorption of the molecules. Thiophene acts by the traditional passivation mechanism, forcing electron density away from the surface. In contrast, pyridine localizes the electron at the surface while leaving it energetically near the conduction band edge. This is because pyridine creates a stronger coordinative bond with a lead atom of the perovskite and has a lower energy unoccupied orbital compared with thiophene due to the more electronegative nitrogen atom relative to thiophene's sulfur. Both molecules reduce two-fold the nonadiabatic coupling and electronic coherence time. A broad range of vibrational modes couple to the electronic subsystem, arising from inorganic and organic components. The simulations reveal the atomistic mechanisms underlying the enhancement of the excited-state lifetime achieved by the perovskite passivation, rationalize the experimental results, and advance our understanding of charge-phonon dynamics in perovskite solar cells.

The role of charged surface residues in the binding ability of small hubs in protein-protein interaction networks

PubMed Central

Patil, Ashwini; Nakamura, Haruki

2007-01-01

Hubs are highly connected proteins in a protein-protein interaction network. Previous work has implicated disordered domains and high surface charge as the properties significant in the ability of hubs to bind multiple proteins. While conformational flexibility of disordered domains plays an important role in the binding ability of large hubs, high surface charge is the dominant property in small hubs. In this study, we further investigate the role of the high surface charge in the binding ability of small hubs in the absence of disordered domains. Using multipole expansion, we find that the charges are highly distributed over the hub surfaces. Residue enrichment studies show that the charged residues in hubs are more prevalent on the exposed surface, with the exception of Arg, which is predominantly found at the interface, as compared to non-hubs. This suggests that the charged residues act primarily from the exposed surface rather than the interface to affect the binding ability of small hubs. They do this through (i) enhanced intra-molecular electrostatic interactions to lower the desolvation penalty, (ii) indirect long – range intermolecular interactions with charged residues on the partner proteins for better complementarity and electrostatic steering, and (iii) increased solubility for enhanced diffusion-controlled rate of binding. Along with Arg, we also find a high prevalence of polar residues Tyr, Gln and His and the hydrophobic residue Met at the interfaces of hubs, all of which have the ability to form multiple types of interactions, indicating that the interfaces of hubs are optimized to participate in multiple interactions. PMID:27857564

The role of charged surface residues in the binding ability of small hubs in protein-protein interaction networks.

PubMed

Patil, Ashwini; Nakamura, Haruki

2007-01-01

Hubs are highly connected proteins in a protein-protein interaction network. Previous work has implicated disordered domains and high surface charge as the properties significant in the ability of hubs to bind multiple proteins. While conformational flexibility of disordered domains plays an important role in the binding ability of large hubs, high surface charge is the dominant property in small hubs. In this study, we further investigate the role of the high surface charge in the binding ability of small hubs in the absence of disordered domains. Using multipole expansion, we find that the charges are highly distributed over the hub surfaces. Residue enrichment studies show that the charged residues in hubs are more prevalent on the exposed surface, with the exception of Arg, which is predominantly found at the interface, as compared to non-hubs. This suggests that the charged residues act primarily from the exposed surface rather than the interface to affect the binding ability of small hubs. They do this through (i) enhanced intra-molecular electrostatic interactions to lower the desolvation penalty, (ii) indirect long - range intermolecular interactions with charged residues on the partner proteins for better complementarity and electrostatic steering, and (iii) increased solubility for enhanced diffusion-controlled rate of binding. Along with Arg, we also find a high prevalence of polar residues Tyr, Gln and His and the hydrophobic residue Met at the interfaces of hubs, all of which have the ability to form multiple types of interactions, indicating that the interfaces of hubs are optimized to participate in multiple interactions.

Contrasting the Influence of Cationic Amino Acids on the Viscosity and Stability of a Highly Concentrated Monoclonal Antibody.

PubMed

Dear, Barton J; Hung, Jessica J; Truskett, Thomas M; Johnston, Keith P

2017-01-01

To explain the effects of cationic amino acids and other co-solutes on the viscosity, stability and protein-protein interactions (PPI) of highly concentrated (≥200 mg/ml) monoclonal antibody (mAb) solutions to advance subcutaneous injection. The viscosities of ≥200 mg/ml mAb1 solutions with various co-solutes and pH were measured by capillary rheometry in some cases up to 70,000 s -1 . The viscosities are analyzed in terms of dilute PPI characterized by diffusion interaction parameters (k D ) from dynamic light scattering (DLS). MAb stability was measured by turbidity and size exclusion chromatography (SEC) after 4 weeks of 40°C storage. Viscosity reductions were achieved by reducing the pH, or adding histidine, arginine, imidazole or camphorsulfonic acid, each of which contains a hydrophobic moiety. The addition of inorganic electrolytes or neutral osmolytes only weakly affected viscosity. Systems with reduced viscosities also tended to be Newtonian, while more viscous systems were shear thinning. Viscosity reduction down to 20 cP at 220 mg/ml mAb1 was achieved with co-solutes that are both charged and contain a hydrophobic interaction domain for sufficient binding to the protein surface. These reductions are related to the DLS diffusion interaction parameter, k D , only after normalization to remove the effect of charge screening. Shear rate profiles demonstrate that select co-solutes reduce protein network formation.

The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somerville, L.; Bareno, J.; Trask, S.

Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

The effect of charging rate on the graphite electrode of commercial lithium-ion cells: A post-mortem study

DOE PAGES

Somerville, L.; Bareno, J.; Trask, S.; ...

2016-10-22

Increased charging rates negatively affect the lifetime of lithium-ion cells by increasing cell resistance and reducing capacity. This work is a post-mortem study of 18650 cells subjected to charge rates of 0.7-, 2-, 4-, and 6-C. For cells charged at 0.7-C to 4-C, this performance degradation is primarily related to surface film thickness with no observable change in surface film chemical composition. However, at charge rates of 6-C, the chemical composition of the surface film changes significantly, suggesting that this change is the reason for the sharper increase in cell resistance compared to the lower charge rates. In addition, wemore » found that surface film formation was not uniform across the electrode. Surface film was thicker and chemically different along the central band of the electrode “jelly roll”. This result is most likely attributable to an increase in temperature that results from non-uniform electrode wetting during manufacture. As a result, this non-uniform change further resulted in active material delamination from the current collector owing to chemical changes to the binder for the cell charged at 6-C.« less

Photocatalytic reduction of CO2 to CO over copper decorated g-C3N4 nanosheets with enhanced yield and selectivity

NASA Astrophysics Data System (ADS)

Shi, Guodong; Yang, Lin; Liu, Zhuowen; Chen, Xiao; Zhou, Jianqing; Yu, Ying

2018-01-01

Photocatalytic reduction of CO2 to fuel has attracted considerable attention due to the consumption of fossil fuels and serious environmental problems. Although there are many photocatalysts reported for CO2 reduction, the improvement of activity and selectivity is still in great need of. In this work, a series of Cu nanoparticle decorated g-C3N4 nanosheets with different Cu loadings were fabricated by a facile secondary calcination and subsequent microwave hydrothermal method. The designed catalysts shown good photocatalytic activity and selectivity for CO2 reduction to CO. The optimal sample exhibited a 3-fold augmentation of the CO yield in comparison with pristine g-C3N4 under visible light. It is revealed that with the loading of Cu nanoparticles, the resulting photocatalyst possessed an improved charge carrier transfer and separation efficiency as well as increased surface reactive sites, resulting in a significant enhancement of CO yield. It is anticipated that the designed Cu/C3N4 photocatalyst may provide new insights for two dimensional layer materials and non-noble particles applied to CO2 reduction.

Decontamination of Hospital Surfaces With Multijet Cold Plasma: A Method to Enhance Infection Prevention and Control?

PubMed

Cahill, Orla J; Claro, Tânia; Cafolla, Attilio A; Stevens, Niall T; Daniels, Stephen; Humphreys, Hilary

2017-10-01

OBJECTIVE To evaluate the efficacy of a multijet cold-plasma system and its efficacy in decontaminating 2 surfaces commonly found in hospitals DESIGN An in vitro study of common causes of healthcare-acquired infection METHODS Log10 9 cultures of methicillin-resistant Staphylococcus aureus, vancomycin-resistant enterococci, extended spectrum β-lactamase-producing Escherichia coli, and Acinetobacter baumannii were applied to 5-cm2 sections of stainless steel and mattress. Human serum albumin (HSA) was used as a proxy marker for organic material, and atomic force microscopy (AFM) was used to study the impact on bacterial cell structure. The inoculated surfaces were exposed to a cold-air-plasma-generating multijet prototype for 15, 20, 30, and 45 seconds. RESULTS After 45 seconds, at least 3 to 4 log reductions were achieved for all bacteria on the mattress, while 3 to 6 log reductions were observed on stainless steel. The presence of HSA had no appreciable effect on bacterial eradication. The surfaces with bacteria exposed to AFM showed significant morphological changes indicative of "etching" due to the action of highly charged ions produced by the plasma. CONCLUSION This multijet cold-plasma prototype has the potential to augment current environmental decontamination approaches but needs further evaluation in a clinical setting to confirm its effectiveness. Infect Control Hosp Epidemiol 2017;38:1182-1187.

[Sorption of microorganisms by fiber materials].

PubMed

Nikovskaia, G N; Gordienko, A S; Globa, L I

1986-01-01

Candida guilliermondii and Escherichia coli cells were adsorbed on glass and basalt fibres with a similar specific surface, but with a different charge. The quantity of adsorbed microorganisms did not depend on the type and charge of a fibre surface. However, cells were adsorbed faster and more firmly on positively charged and uncharged fibres than on negatively charged fibres.

Transistor and memory devices based on novel organic and biomaterials

NASA Astrophysics Data System (ADS)

Tseng, Jia-Hung

Organic semiconductor devices have aroused considerable interest because of the enormous potential in many technological applications. Organic electroluminescent devices have been extensively applied in display technology. Rapid progress has also been made in transistor and memory devices. This thesis considers aspects of the transistor based on novel organic single crystals and memory devices using hybrid nanocomposites comprising polymeric/inorganic nanoparticles, and biomolecule/quantum dots. Organic single crystals represent highly ordered structures with much less imperfections compared to amorphous thin films for probing the intrinsic charge transport in transistor devices. We demonstrate that free-standing, thin organic single crystals with natural flexing ability can be fabricated as flexible transistors. We study the surface properties of the organic crystals to determine a nearly perfect surface leading to high performance transistors. The flexible transistors can maintain high performance under reversible bending conditions. Because of the high quality crystal technique, we further develop applications on organic complementary circuits and organic single crystal photovoltaics. In the second part, two aspects of memory devices are studied. We examine the charge transfer process between conjugated polymers and metal nanoparticles. This charge transfer process is essential for the conductance switching in nanoseconds to induce the memory effect. Under the reduction condition, the charge transfer process is eliminated as well as the memory effect, raising the importance of coupling between conjugated systems and nanoparticle accepters. The other aspect of memory devices focuses on the interaction of virus biomolecules with quantum dots or metal nanoparticles in the devices. We investigate the impact of memory function on the hybrid bio-inorganic system. We perform an experimental analysis of the charge storage activation energy in tobacco mosaic virus with platinum nanoparticles. It is established that the effective barrier height in the materials systems needs to be further engineered in order to have sufficiently long retention times. Finally other novel architectures such as negative differential resistance devices and high density memory arrays are investigated for their influence on memory technology.

Charge collection kinetics on ferroelectric polymer surface using charge gradient microscopy

DOE PAGES

Choi, Yoon-Young; Tong, Sheng; Ducharme, Stephen P.; ...

2016-05-03

Here, a charge gradient microscopy (CGM) probe was used to collect surface screening charges on poly(vinylidene fluoride-trifluoroethylene) [P(VDF-TrFE)] thin films. These charges are naturally formed on unscreened ferroelectric domains in ambient condition. The CGM data were used to map the local electric current originating from the collected surface charges on the poled ferroelectric domains in the P(VDF-TrFE) thin films. Both the direction and amount of the collected current were controlled by changing the polarity and area of the poled domains. The endurance of charge collection by rubbing the CGM tip on the polymer film was limited to 20 scan cycles,more » after which the current reduced to almost zero. This degradation was attributed to the increase of the chemical bonding strength between the external screening charges and the polarization charges. Once this degradation mechanism is mitigated, the CGM technique can be applied to efficient energy harvesting devices using polymer ferroelectrics.« less

Surface Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

PubMed Central

Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

2008-01-01

Surface assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to oxide surface in atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to the half of that for the collision rate. PMID:16956285

Role of Surface Charge Density in Nanoparticle-templated Assembly of Bromovirus Protein Cages

PubMed Central

Daniel, Marie-Christine; Tsvetkova, Irina B.; Quinkert, Zachary T.; Murali, Ayaluru; De, Mrinmoy; Rotello, Vincent M.; Kao, C. Cheng; Dragnea, Bogdan

2010-01-01

Self-assembling icosahedral protein cages have potencially useful physical and chemical characteristics for a variety of nanotechnology applications, ranging from therapeutic or diagnostic vectors to building blocks for hierarchical materials. For application-specific functional control of protein cage assemblies, a deeper understanding of the interaction between the protein cage and its payload is necessary. Protein-cage encapsulated nanoparticles, with their well-defined surface chemistry, allow for systematic control over key parameters of encapsulation such as the surface charge, hydrophobicity, and size. Independent control over these variables allows experimental testing of different assembly mechanism models. Previous studies done with Brome mosaic virus capsids and negatively-charged gold nanoparticles indicated that the result of the self-assembly process depends on the diameter of the particle. However, in these experiments, the surface-ligand density was maintained at saturation levels, while the total charge and the radius of curvature remained coupled variables, making the interpretation of the observed dependence on the core size difficult. The current work furnishes evidence of a critical surface charge density for assembly through an analysis aimed at decoupling the surface charge the core size. PMID:20575505

In Vitro Biocompatibility of Si Alloyed Multi-Principal Element Carbide Coatings

PubMed Central

Vladescu, Alina; Titorencu, Irina; Dekhtyar, Yuri; Jinga, Victor; Pruna, Vasile; Balaceanu, Mihai; Dinu, Mihaela; Pana, Iulian; Vendina, Viktorija

2016-01-01

In the current study, we have examined the possibility to improve the biocompatibility of the (TiZrNbTaHf)C through replacement of either Ti or Ta by Si. The coatings were deposited on Si and 316L stainless steel substrates by magnetron sputtering in an Ar+CH4 mixed atmosphere and were examined for elemental composition, chemical bonds, surface topography, surface electrical charge and biocompatible characteristics. The net surface charge was evaluated at nano and macroscopic scale by measuring the electrical potential and work function, respectively. The biocompatible tests comprised determination of cell viability and cell attachment to the coated surface. The deposited coatings had C/(metal+Si) ratios close to unity, while a mixture of metallic carbide, free-carbon and oxidized species formed on the film surface. The coatings’ surfaces were smooth and no influence of surface roughness on electrical charge or biocompatibility was found. The biocompatible characteristics correlated well with the electrical potential/work function, suggesting a significant role of surface charge in improving biocompatibility, particularly cell attachment to coating's surface. Replacement of either Ti or Ta by Si in the (TiZrNbTaHf)C coating led to an enhanced surface electrical charge, as well as to superior biocompatible properties, with best results for the (TiZrNbSiHf)C coating. PMID:27571361

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

NASA Astrophysics Data System (ADS)

Wang, Weiwang; Li, Shengtao; Min, Daomin

2016-04-01

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al2O3 nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al2O3 nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and the strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al2O3 nanodielectrics is improved.

Plasmonic tunnel junctions for single-molecule redox chemistry.

PubMed

de Nijs, Bart; Benz, Felix; Barrow, Steven J; Sigle, Daniel O; Chikkaraddy, Rohit; Palma, Aniello; Carnegie, Cloudy; Kamp, Marlous; Sundararaman, Ravishankar; Narang, Prineha; Scherman, Oren A; Baumberg, Jeremy J

2017-10-20

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities generate hot charge carriers, which can catalyse chemical reactions or induce redox processes in molecules located within the plasmonic hotspots. Here, surface-enhanced Raman spectroscopy allows us to track these hot-electron-induced chemical reduction processes in a series of different aromatic molecules. We demonstrate that by increasing the tunnelling barrier height and the dephasing strength, a transition from coherent to hopping electron transport occurs, enabling observation of redox processes in real time at the single-molecule level.

Effects of oxygen radicals in low-pressure surface-wave plasma on sterilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagatsu, Masaaki; Terashita, Fumie; Nonaka, Hiroyuki

2005-05-23

The effects of oxygen radicals on sterilization were studied using a 2.45 GHz surface-wave oxygen plasma. A population of 1.5x10{sup 6} Bacillus stearothermophilus spores was irradiated for 3 min or more with oxygen plasma, generated at pressures between 6 and 14 Pa. The decimal reduction value (D value), a measure of the effectiveness of sterilization, was determined to be about 15-25 s. Using only oxygen radicals, excluding all charged particles, the 1.5x10{sup 6} spores were sterilized with a D value of 30-45 s after 5 min or more of irradiation. On scanning electron microscopy, the length and width of themore » spores changed significantly due to chemical etching by oxygen radicals.« less

42 CFR 413.13 - Amount of payment if customary charges for services furnished are less than reasonable costs.

Code of Federal Regulations, 2011 CFR

2011-10-01

....330 et seq. (d) Exclusions from reasonable cost. For purposes of comparison with customary charges... education costs. (e) Reductions in customary charges. Customary charges are reduced in proportion to the... services, with the exception of DME, are considered together. (iii) Graduate medical education. When making...

42 CFR 413.13 - Amount of payment if customary charges for services furnished are less than reasonable costs.

Code of Federal Regulations, 2013 CFR

2013-10-01

....330 et seq. (d) Exclusions from reasonable cost. For purposes of comparison with customary charges... education costs. (e) Reductions in customary charges. Customary charges are reduced in proportion to the... services, with the exception of DME, are considered together. (iii) Graduate medical education. When making...

42 CFR 413.13 - Amount of payment if customary charges for services furnished are less than reasonable costs.

Code of Federal Regulations, 2012 CFR

2012-10-01

....330 et seq. (d) Exclusions from reasonable cost. For purposes of comparison with customary charges... education costs. (e) Reductions in customary charges. Customary charges are reduced in proportion to the... services, with the exception of DME, are considered together. (iii) Graduate medical education. When making...

Translocation of double strand DNA into a biological nanopore

NASA Astrophysics Data System (ADS)

Chatkaew, Sunita; Mlayeh, Lamia; Leonetti, Marc; Homble, Fabrice

2009-03-01

Translocation of double strand DNA across a unique mitochondrial biological nanopore (VDAC) is observed by an electrophysiological method. Characteristics of opened and sub-conductance states of VDAC are studied. When the applied electric potential is beyond ± 20 mV, VDAC transits to a sub-conductance state. Plasmids (circular double strand DNA) with a diameter greater than that of the channel shows the current reduction into the channel during the interaction but the state with zero-current is not observed. On the contrary, the interaction of linear double strand DNA with the channel shows the current reduction along with the zero-current state. These show the passages of linear double strand DNA across the channel and the electrostatic effect due to the surface charges of double strand DNA and channel for circular and linear double strand DNA.

Adsorption of reovirus by minerals and soils.

PubMed Central

Moore, R S; Taylor, D H; Reddy, M M; Sturman, L S

1982-01-01

Adsorption of [35S]methionine-labeled reovirus by 30 dry soils, minerals, and finely ground rocks suspended in synthetic freshwater at pH 7 was investigated to determine the conditions necessary for optimum virus removal during land application of wastewaters. All of the minerals and soils studied were excellent adsorbents of reovirus, with greater than 99% of the virus adsorbed after 1 h at 4 degrees C. Thereafter, virus remaining in suspension was significantly inactivated, and within 24 h a three to five log10 reduction in titer occurred. The presence of divalent cations, i.e., Ca2+ and Mg2+, in synthetic freshwater enhanced removal, whereas soluble organic matter decreased the amount of virus adsorbed in secondary effluent. The amount of virus adsorbed by these substrates was inversely correlated with the amount of organic matter, capacity to adsorb cationic polyelectrolyte, and electrophoretic mobility. Adsorption increased with increasing available surface area, as suspended infectivity was reduced further by the more finely divided substrates. However, the organic content of the soils reduced the level of infectious virus adsorbed below that expected from surface area measurements alone. The inverse correlation between virus adsorption and substrate capacity for cationic polyelectrolyte indicates that the adsorption of infectious reovirus particles is predominately a charged colloidal particle-charged surface interaction. Thus, adsorption of polyelectrolyte may be useful in predicting the fate of viruses during land application of sewage effluents and sludges. PMID:7149717

Magnetic Photocatalyst BiVO₄/Mn-Zn ferrite/Reduced Graphene Oxide: Synthesis Strategy and Its Highly Photocatalytic Activity.

PubMed

Xie, Taiping; Li, Hui; Liu, Chenglun; Yang, Jun; Xiao, Tiancun; Xu, Longjun

2018-05-29

Magnetic photocatalyst BiVO₄/Mn-Zn ferrite (Mn 1- x Zn x Fe₂O₄)/reduced graphene oxide (RGO) was synthesized by a simple calcination and reduction method. The magnetic photocatalyst held high visible light-absorption ability with low band gap energy and wide absorption wavelength range. Electrochemical impedance spectroscopies illustrated good electrical conductivity which indicated low charge-transfer resistance due to incorporation of Mn 1- x Zn x Fe₂O₄ and RGO. The test of photocatalytic activity showed that the degradation ratio of rhodamine B (RhB) reached 96.0% under visible light irradiation after only 1.5 h reaction. The photocatalytic mechanism for the prepared photocatalyst was explained in detail. Here, the incorporation of RGO enhanced the specific surface area compared with BiVO4/Mn 1- x Zn x Fe₂O₄.The larger specific surface area provided more active surface sites, more free space to improve the mobility of photo-induced electrons, and further facilitated the effective migration of charge carriers, leading to the remarkable improvement of photocatalytic performance. Meanwhile, RGO was the effective acceptor as well as transporter of photo-generated electron hole pairs. •O₂ - was the most active species in the photocatalytic reaction. BiVO₄/Mn 1- x Zn x Fe₂O₄/RGO had quite a wide application in organic contaminants removal or environmental pollution control.

Effects of O 2 and N 2/H 2 plasma treatments on the neuronal cell growth on single-walled carbon nanotube paper scaffolds

NASA Astrophysics Data System (ADS)

Yoon, Ok Ja; Lee, Hyun Jung; Jang, Yeong Mi; Kim, Hyun Woo; Lee, Won Bok; Kim, Sung Su; Lee, Nae-Eung

2011-08-01

The O 2 and N 2/H 2 plasma treatments of single-walled carbon nanotube (SWCNT) papers as scaffolds for enhanced neuronal cell growth were conducted to functionalize their surfaces with different functional groups and to roughen their surfaces. To evaluate the effects of the surface roughness and functionalization modifications of the SWCNT papers, we investigated the neuronal morphology, mitochondrial membrane potential, and acetylcholine/acetylcholinesterase levels of human neuroblastoma during SH-SY5Y cell growth on the treated SWCNT papers. Our results demonstrated that the plasma-chemical functionalization caused changes in the surface charge states with functional groups with negative and positive charges and then the increased surface roughness enhanced neuronal cell adhesion, mitochondrial membrane potential, and the level of neurotransmitter in vitro. The cell adhesion and mitochondrial membrane potential on the negatively charged SWCNT papers were improved more than on the positively charged SWCNT papers. Also, measurements of the neurotransmitter level showed an enhanced acetylcholine level on the negatively charged SWCNT papers compared to the positively charged SWCNT papers.

Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

PubMed

Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

2010-05-05

A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

To-date spacecraft applications and demonstration testing results, and future product development for new molecular adsorber technologies

NASA Technical Reports Server (NTRS)

Thomson, Shaun; Hansen, Patricia; Straka, Sharon; Chen, Philip; Triolo, Jack; Bettini, Ron; Carosso, Paolo; Carosso, Nancy

1997-01-01

The use of molecular adsorbers, in order to aid in the reduction of the spacecraft contamination levels, is discussed. Molecular adsorbers are characterized by an extremely large surface area, molecularly-porous substructure, and processing charged sites capable of retaining molecular contaminant species. Molecular adsorbers were applied on two Hubble Space Telescope servicing missions, as well as on the tropical rainfall measuring mission. The use of molecular adsorbers carries the potential for low cost, easy fabrication and integration of reliable means for reducing the contamination level around spacecraft.

Applying simulation model to uniform field space charge distribution measurements by the PEA method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Y.; Salama, M.M.A.

1996-12-31

Signals measured under uniform fields by the Pulsed Electroacoustic (PEA) method have been processed by the deconvolution procedure to obtain space charge distributions since 1988. To simplify data processing, a direct method has been proposed recently in which the deconvolution is eliminated. However, the surface charge cannot be represented well by the method because the surface charge has a bandwidth being from zero to infinity. The bandwidth of the charge distribution must be much narrower than the bandwidths of the PEA system transfer function in order to apply the direct method properly. When surface charges can not be distinguished frommore » space charge distributions, the accuracy and the resolution of the obtained space charge distributions decrease. To overcome this difficulty a simulation model is therefore proposed. This paper shows their attempts to apply the simulation model to obtain space charge distributions under plane-plane electrode configurations. Due to the page limitation for the paper, the charge distribution originated by the simulation model is compared to that obtained by the direct method with a set of simulated signals.« less

Control of single-electron charging of metallic nanoparticles onto amorphous silicon surface.

PubMed

Weis, Martin; Gmucová, Katarína; Nádazdy, Vojtech; Capek, Ignác; Satka, Alexander; Kopáni, Martin; Cirák, Július; Majková, Eva

2008-11-01

Sequential single-electron charging of iron oxide nanoparticles encapsulated in oleic acid/oleyl amine envelope and deposited by the Langmuir-Blodgett technique onto Pt electrode covered with undoped hydrogenated amorphous silicon film is reported. Single-electron charging (so-called quantized double-layer charging) of nanoparticles is detected by cyclic voltammetry as current peaks and the charging effect can be switched on/off by the electric field in the surface region induced by the excess of negative/positive charged defect states in the amorphous silicon layer. The particular charge states in amorphous silicon are created by the simultaneous application of a suitable bias voltage and illumination before the measurement. The influence of charged states on the electric field in the surface region is evaluated by the finite element method. The single-electron charging is analyzed by the standard quantized double layer model as well as two weak-link junctions model. Both approaches are in accordance with experiment and confirm single-electron charging by tunnelling process at room temperature. This experiment illustrates the possibility of the creation of a voltage-controlled capacitor for nanotechnology.

Electrification of particulate entrained fluid flows-Mechanisms, applications, and numerical methodology

NASA Astrophysics Data System (ADS)

Wei, Wei; Gu, Zhaolin

2015-10-01

Particulates in natural and industrial flows have two basic forms: liquid (droplet) and solid (particle). Droplets would be charged in the presence of the applied electric field (e.g. electrospray). Similar to the droplet charging, particles can also be charged under the external electric field (e.g. electrostatic precipitator), while in the absence of external electric field, tribo-electrostatic charging is almost unavoidable in gas-solid two-phase flows due to the consecutive particle contacts (e.g. electrostatic in fluidized bed or wind-blown sand). The particle charging may be beneficial, or detrimental. Although electrostatics in particulate entrained fluid flow systems have been so widely used and concerned, the mechanisms of particulate charging are still lack of a thorough understanding. The motivation of this review is to explore a clear understanding of particulate charging and movement of charged particulate in two-phase flows, by summarizing the electrification mechanisms, physical models of particulate charging, and methods of charging/charged particulate entrained fluid flow simulations. Two effective methods can make droplets charged in industrial applications: corona charging and induction charging. The droplet charge to mass ratio by corona charging is more than induction discharge. The particle charging through collisions could be attributed to electron transfer, ion transfer, material transfer, and/or aqueous ion shift on particle surfaces. The charges on charged particulate surface can be measured, nevertheless, the charging process in nature or industry is difficult to monitor. The simulation method might build a bridge of investigating from the charging process to finally charged state on particulate surface in particulate entrained fluid flows. The methodology combining the interface tracking under the action of the applied electric with the fluid flow governing equations is applicable to the study of electrohydrodynamics problems. The charge distribution and mechanical behaviors of liquid surface can be predicted by using this method. The methodology combining particle charging model with Computational Fluid Dynamics (CFD) and Discrete element method (DEM) is applicable to study the particle charging/charged processes in gas-solid two phase flows, the influence factors of particle charging, such as gas-particle interaction, contact force, contact area, and various velocities, are described systematically. This review would explore a clear understanding of the particulate charging and provide theoretical references to control and utilize the charging/charged particulate entrained fluid system.

Partially Oxidized SnS2 Atomic Layers Achieving Efficient Visible-Light-Driven CO2 Reduction.

PubMed

Jiao, Xingchen; Li, Xiaodong; Jin, Xiuyu; Sun, Yongfu; Xu, Jiaqi; Liang, Liang; Ju, Huanxin; Zhu, Junfa; Pan, Yang; Yan, Wensheng; Lin, Yue; Xie, Yi

2017-12-13

Unraveling the role of surface oxide on affecting its native metal disulfide's CO 2 photoreduction remains a grand challenge. Herein, we initially construct metal disulfide atomic layers and hence deliberately create oxidized domains on their surfaces. As an example, SnS 2 atomic layers with different oxidation degrees are successfully synthesized. In situ Fourier transform infrared spectroscopy spectra disclose the COOH* radical is the main intermediate, whereas density-functional-theory calculations reveal the COOH* formation is the rate-limiting step. The locally oxidized domains could serve as the highly catalytically active sites, which not only benefit for charge-carrier separation kinetics, verified by surface photovoltage spectra, but also result in electron localization on Sn atoms near the O atoms, thus lowering the activation energy barrier through stabilizing the COOH* intermediates. As a result, the mildly oxidized SnS 2 atomic layers exhibit the carbon monoxide formation rate of 12.28 μmol g -1 h -1 , roughly 2.3 and 2.6 times higher than those of the poorly oxidized SnS 2 atomic layers and the SnS 2 atomic layers under visible-light illumination. This work uncovers atomic-level insights into the correlation between oxidized sulfides and CO 2 reduction property, paving a new way for obtaining high-efficiency CO 2 photoreduction performances.

Characterization of triboelectrically charged particles deposited on dielectric surfaces

NASA Astrophysics Data System (ADS)

Nesterov, A.; Löffler, F.; Cheng, Yun-Chien; Torralba, G.; König, K.; Hausmann, M.; Lindenstruth, V.; Stadler, V.; Bischoff, F. R.; Breitling, F.

2010-04-01

A device for the measurement of q/m-values and charge degradation of triboelectrically charged particles deposited on a surface was developed. The setup is based on the integration of currents, which are induced in a Faraday cage by insertion of a solid support covered with charged particles. The conductivity of different particle supports was taken into account. The 'blow-off' method, in which the particles are first deposited, and then blown off using an air stream, can be used for characterization of triboelectric properties of particles relative to different surfaces.

Dust Grain Charge in the Lunar Environment

NASA Astrophysics Data System (ADS)

Vaverka, Jakub; Richterova, Ivana; Vysinka, Marek; Pavlu, Jiri; Safrankova, Jana; Nemecek, Zdenek

2014-05-01

Interaction of a lunar surface with solar wind and magnetosphere plasmas leads to it charging by several processes as photoemission, a collection of primary particles and secondary electron emission. Nevertheless, charging of the lunar surface is complicated by a presence of crustal magnetic anomalies with can generate a "mini-magnetosphere" capable for more or less complete shielding the surface. On the other hand, shielding of solar light and plasma particles by rocks and craters can also locally influence the surface potential as well as a presence of a plasma wake strongly changes this potential at the night side of the Moon. A typical surface potential varies from slightly positive (dayside) to negative values of the order of several hundred of volts (night side). At the night side, negative potentials can reach -4 kV during solar energetic particle (SEP) events. Recent measurements of the surface potential by Lunar Prospector and Artemis spacecraft have shown surprisingly high negative dayside surface potentials (-500 V) during the magnetotail crossings as well as the positive surface potential higher than 100 V. One possible explanation is its non-monotonic profile above a surface where the potential minimum is formed by the space charge. Dust grains presented in this complicated environment are also charged by similar processes as the lunar surface. A strong dependence of the secondary electron yield on the grain size can significantly influence dust charging mainly in the Earth's plasma sheet where an equilibrium grain potential can by different than the surface potential and can reach even the opposite sign. This process can lead to levitation of dust above a surface observed by the Surveyor spacecraft.

Development of Charge to Mass Ratio Microdetector for Future Mars Mission

NASA Technical Reports Server (NTRS)

Chen, Yuan-Lian Albert

2003-01-01

The Mars environment comprises a dry, cold and low air pressure atmosphere with low gravity (0.38g) and high resistivity soil. The global dust storms that cover a large portion of Mars are observed often from Earth. This environment provides an ideal condition for turboelectric charging. The extremely dry conditions on the Martian surface have raised concerns that electrostatic charge buildup will not be dissipated easily. If turboelectrically generated charge cannot be dissipated or avoided, then dust will accumulate on charged surfaces and electrostatic discharge may cause hazards for future exploration missions. The low surface on Mars helps to prolong the charge decay on the dust particles and soil. To better understanding the physics of Martian charged dust particles is essential to future Mars missions. We research and design two sensors, velocity/charge sensor and PZT momentum sensors, to measure the velocity distribution, charge distribution and mass distribution of Martian wed dust particles. These sensors are fabricated at NASA Kenney Space Center, Electrostatic and Surface Physics Laboratory. The sensors are calibrated. The momentum sensor is capable to measure 45 pan size particles. The designed detector is very simple, robust, without moving parts, and does not require a high voltage power supply. Two sensors are combined to form the Dust Microdetector - CHAL.

The Review on the Charge Distribution on the Conductor Surface

ERIC Educational Resources Information Center

Matehkolaee, M. Jafari; Asrami, A. Naderi

2013-01-01

In this paper we have a full review on the surface charge density at disordered conductor surfaces. Basically, reading text books does not resolve ambiguities in this field. As far as is possible, we have tried to the concepts easier to turn. In fact we will answer two questions. One of them is that why do charges tend to go where the curvature is…

On the dependence of charge density on surface curvature of an isolated conductor

NASA Astrophysics Data System (ADS)

Bhattacharya, Kolahal

2016-03-01

A study of the relation between the electrostatic charge density at a point on a conducting surface and the curvature of the surface (at that point) is presented. Two major papers in the scientific literature on this topic are reviewed and the apparent discrepancy between them is resolved. Hence, a step is taken towards obtaining a general analytic formula for relating the charge density with surface curvature of conductors. The merit of this formula and its limitations are discussed.

Towards a More Complete Picture: Dissimilatory Metal Reduction by Anaeromyxobacter Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loeffler, Frank E.

2005-06-01

Towards a More Complete Picture: Dissimilatory Metal Reduction by Anaeromyxobacter Species The overarching goal of this 3-year project is to explore uranium reduction in Anaeromyxobacter species. Specifically, we explore the physiological requirements of available Anaeromyxobacter isolates, design molecular biology tools to detect and quantify Anaeromyxobacter in pure cultures, consortia, and environmental samples, assess their diversity, distribution, and abundance in the environment, including DOE sites, and attempt the isolation of additional Anaeromyxobacter species from the Oak Ridge Field Research Center (FRC). The performers on this project include Frank Loeffler (PI), Robert Sanford (Co-PI), Qingzhong Wu (postdoc), Sara Henry (graduate student withmore » fellowship, no charges to NABIR project), Ivy Thomson (graduate student, no charges to NABIR project), and Ryan Wagner (''Special Topics'' bioinformatics undergraduate student, no charges to NABIR project). Exploratory MALDI-TOF MS experiments for the specific detection of Anaeromyxobacter species were performed by Kerry Preston (graduate student, no charges to NABIR project).« less

Charging of particles on a surface

NASA Astrophysics Data System (ADS)

Heijmans, Lucas; Nijdam, Sander

2016-09-01

This contribution focusses on the seemingly easy problem of the charging of micrometer sized particles on a substrate in a plasma. This seems trivial, because much is known about both the charging of surfaces near a plasma and of particles in the plasma bulk. The problem, however, becomes much more complicated when the particle is on the substrate surface. The charging currents to the particle are then highly altered by the substrate plasma sheath. Currently there is no consensus in literature about the resulting particle charge. We shall present both experimental measurements and numerical simulations of the charge on these particles. The experimental results are acquired by measuring the particle acceleration in an external electric field. For the simulations we have used our specially developed model. We shall compare these results to other estimates found in literature.

Enhanced electrohydrodynamic force generation in a two-stroke cycle dielectric-barrier-discharge plasma actuator

NASA Astrophysics Data System (ADS)

Sato, Shintaro; Takahashi, Masayuki; Ohnishi, Naofumi

2017-05-01

An approach for electrohydrodynamic (EHD) force production is proposed with a focus on a charge cycle on a dielectric surface. The cycle, consisting of positive-charging and neutralizing strokes, is completely different from the conventional methodology, which involves a negative-charging stroke, in that the dielectric surface charge is constantly positive. The two-stroke charge cycle is realized by applying a DC voltage combined with repetitive pulses. Simulation results indicate that the negative pulse eliminates the surface charge accumulated during constant voltage phase, resulting in repetitive EHD force generation. The time-averaged EHD force increases almost linearly with increasing repetitive pulse frequency and becomes one order of magnitude larger than that driven by the sinusoidal voltage, which has the same peak-to-peak voltage.

Simulation study of spheroidal dust gains charging: Applicable to dust grain alignment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zahed, H.; Sobhanian, S.; Mahmoodi, J.

2006-09-15

The charging process of nonspherical dust grains in an unmagnetized plasma as well as in the presence of a magnetic field is studied. It is shown that unlike the spherical dust grain, due to nonhomogeneity of charge distribution on the spheroidal dust surface, the resultant electric forces on electrons and ions are different. This process produces some surface charge density gradient on the nonspherical grain surface. Effects of a magnetic field and other plasma parameters on the properties of the dust particulate are studied. It has been shown that the alignment direction could be changed or even reversed with themore » magnetic field and plasma parameters. Finally, the charge distribution on the spheroidal grain surface is studied for different ambient parameters including plasma temperature, neutral collision frequency, and the magnitude of the magnetic field.« less

Model simulations of the adsorption of statherin to solid surfaces: Effects of surface charge and hydrophobicity

NASA Astrophysics Data System (ADS)

Skepö, M.

2008-11-01

The structural properties of the salivary protein statherin upon adsorption have been examined using a coarse-grained model and Monte Carlo simulation. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. To mimic hydrophobically modified surfaces, an extra short-ranged interaction was implemented between the amino acids and the surface. It has been shown that the adsorption and the thickness of the adsorbed layer are determined by (i) the affinity for the surface, i.e., denser layer with an extrashort-ranged potential, and (ii) the distribution of the charges along the chain. If all the amino acids have a high affinity for the surface, the protein adsorbs in a train conformation, if the surface is negatively charged the protein adsorbs in a tail-train conformation, whereas if the surface is positively charged the protein adsorbs in a loop conformation. The latter gives rise to a more confined adsorbed layer.

Charge Storage, Conductivity and Charge Profiles of Insulators as Related to Spacecraft Charging

NASA Technical Reports Server (NTRS)

Dennison, J. R.; Swaminathan, Prasanna; Frederickson, A. R.

2004-01-01

Dissipation of charges built up near the surface of insulators due to space environment interaction is central to understanding spacecraft charging. Conductivity of insulating materials is key to determine how accumulated charge will distribute across the spacecraft and how rapidly charge imbalance will dissipate. To understand these processes requires knowledge of how charge is deposited within the insulator, the mechanisms for charge trapping and charge transport within the insulator, and how the profile of trapped charge affects the transport and emission of charges from insulators. One must consider generation of mobile electrons and holes, their trapping, thermal de-trapping, mobility and recombination. Conductivity is more appropriately measured for spacecraft charging applications as the "decay" of charge deposited on the surface of an insulator, rather than by flow of current across two electrodes around the sample. We have found that conductivity determined from charge storage decay methods is 102 to 104 smaller than values obtained from classical ASTM and IEC methods for a variety of thin film insulating samples. For typical spacecraft charging conditions, classical conductivity predicts decay times on the order of minutes to hours (less than typical orbit periods); however, the higher charge storage conductivities predict decay times on the order of weeks to months leading to accumulation of charge with subsequent orbits. We found experimental evidence that penetration profiles of radiation and light are exceedingly important, and that internal electric fields due to charge profiles and high-field conduction by trapped electrons must be considered for space applications. We have also studied whether the decay constants depend on incident voltage and flux or on internal charge distributions and electric fields; light-activated discharge of surface charge to distinguish among differing charge trapping centers; and radiation-induced conductivity. Our experiments also show that "Malter" electron emission occurs for hours after turning off the electron beam. This Malter emission similar to emission due to negative electron affinity in semiconductors is a result of the prior radiation or optical excitations of valence electrons and their slow drift among traps towards the surface where they are subsequently emitted. This work is supported through funding from the NASA Space Environments and Effects Program.

Investigations of charged particle motion on the surfaces of dusty, airless solar system bodies (Invited)

NASA Astrophysics Data System (ADS)

Dove, A.; Colwell, J. E.

2013-12-01

Dynamic charging conditions exist on the dusty surfaces of planetary bodies such as the Moon, asteroids, and the moons of Mars. On these so-called 'airless bodies', the motions of dust particles above the surface become complex due to grain-grain and grain-plasma interactions. For example, tribocharging and other charge transfer processes can occur due to relative dust grain movements, and charged dust grains immersed in plasma interact with local electromagnetic forces. This is thought to lead to effects such as the lunar 'horizon glow,' (Rennilson and Criswell, 1974, The Moon, 10) and potential dusty 'fountains' above the lunar surface (Stubbs et al., 2006, Adv. Sp. Res., 37). Regolith grains can be mobilized by impacts or other mechanical disturbances, or simply by the Coulomb force acting on grains. Previous work has increased our theoretical understanding of the behavior of charged particles in these low-gravity environments (i.e. Poppe and Horanyi, 2010, JGR, A115; Colwell et al., 2007, Rev. Geophys., 45 (and references therein)). Experimental work has also analyzed grain surface charging due to plasma or tribocharging (Sickafoose et al., 2001, JGR, 106) and the motion of grains on surfaces in the presence of an electric field (Wang et al., 2009, JGR, 114). Occasionally, there is disagreement between theoretical predictions and observations. We present the results of new laboratory experiments aimed at understanding particle charging and the dynamics of charged particles on the surfaces of airless bodies. In the initial experiments, we analyze the motion of particles in the presence of an electric field in vacuum, either in a bell-jar or in a 0.75-second microgravity drop tower experiment box. Prior to motion, particles may be charged due to triboelectric effects, plasma interactions, or a combination of the two. Motion is induced by shaking or by low-velocity impacts in order to simulate the natural motion of slow-moving objects on regolith surfaces, or induced motion such as that due to a spacecraft. The resulting particle dynamics are tracked using high-speed, high-resolution video. Future exploration on or near the surfaces of airless bodies will certainly experience complications arising from these dusty environments, where particles may contaminate or interfere with the operation of almost any mechanical equipment. By exploring the dynamic behavior of charged particles in these environments, we can work towards solutions that will enable exploration.

Differential photoelectric charging of nonconducting surfaces in space. [on sunlit strip

NASA Technical Reports Server (NTRS)

Pelizzari, M. A.; Criswell, D. R.

1978-01-01

The photoelectric charging caused by an infinitely long strip of sunlight across a nonconducting plane is studied by use of a model which contains an electrical cutoff radius, and the results of numerical calculations are presented. The model simulates charging of a sunlit area with dimensions equal to the strip's width, exposed to a plasma with a comparatively large Debye length. Uniform potential is quickly established on a uniformly sunlit strip as a result of charge redistribution by low-energy photoelectrons. The results are in accord with a theoretical surface conductivity derived for photoelectron sheaths above highly charged sunlit areas. The surface potential, which drops sharply across the sunlight-shadow boundary, is discussed.

On the theoretical description of weakly charged surfaces.

PubMed

Wang, Rui; Wang, Zhen-Gang

2015-03-14

It is widely accepted that the Poisson-Boltzmann (PB) theory provides a valid description for charged surfaces in the so-called weak coupling limit. Here, we show that the image charge repulsion creates a depletion boundary layer that cannot be captured by a regular perturbation approach. The correct weak-coupling theory must include the self-energy of the ion due to the image charge interaction. The image force qualitatively alters the double layer structure and properties, and gives rise to many non-PB effects, such as nonmonotonic dependence of the surface energy on concentration and charge inversion. In the presence of dielectric discontinuity, there is no limiting condition for which the PB theory is valid.

Dynamics of charges and solitons

NASA Astrophysics Data System (ADS)

Barros, Manuel; Ferrández, Ángel; Garay, Óscar J.

2018-02-01

We first show that trajectories traced by charges moving in rotational magnetic fields are, basically, the non-parallel geodesics of surfaces of revolution with coincident axis. Thus, people living in a surface of revolution are not able to sense the magnetic Hall effect induced by the surrounding magnetic field and perceive charges as influenced, exclusively, by the gravity action on the surface of revolution. Secondly, the extended Hasimoto transformations are introduced and then used to identify trajectories of charges moving through a Killing rotational magnetic field in terms of non-circular elastic curves. As a consequence, we see that in this case charges evolve along trajectories which are obtained as extended Hasimoto transforms of solitons of the filament equation.

Charged plate in asymmetric electrolytes: One-loop renormalization of surface charge density and Debye length due to ionic correlations.

PubMed

Ding, Mingnan; Lu, Bing-Sui; Xing, Xiangjun

2016-10-01

Self-consistent field theory (SCFT) is used to study the mean potential near a charged plate inside a m:-n electrolyte. A perturbation series is developed in terms of g=4πκb, where band1/κ are Bjerrum length and bare Debye length, respectively. To the zeroth order, we obtain the nonlinear Poisson-Boltzmann theory. For asymmetric electrolytes (m≠n), the first order (one-loop) correction to mean potential contains a secular term, which indicates the breakdown of the regular perturbation method. Using a renormalizaton group transformation, we remove the secular term and obtain a globally well-behaved one-loop approximation with a renormalized Debye length and a renormalized surface charge density. Furthermore, we find that if the counterions are multivalent, the surface charge density is renormalized substantially downwards and may undergo a change of sign, if the bare surface charge density is sufficiently large. Our results agrees with large MC simulation even when the density of electrolytes is relatively high.

Analysis of Electrokinetic Mixing Using AC Electric Field and Patchwise Surface Heterogeneities

NASA Astrophysics Data System (ADS)

Luo, Win-Jet; Yarn, Kao-Feng; Hsu, Shou-Ping

2007-04-01

In this paper, the authors investigate the use of an applied AC electric field and microchannel surface heterogeneities to carry out the microfluidic mixing of two-dimensional, time-dependent electroosmotic flows. The time-dependent flow fields within the microchannel are simulated using the backwards-Euler time-stepping numerical method. The mixing efficiencies obtained in microchannels with two different patchwise surface heterogeneity patterns are investigated. In general, the results show that the application of an AC electric field significantly reduces the required mixing length compared with the use of a DC electric field. Furthermore, the presence of oppositely charged surface heterogeneities on the microchannel walls results in the formation of localized flow circulation regions within the bulk flow. These circulation regions grow and decay periodically in accordance with the periodic variation of the AC electric field intensity and provide an effective means of enhancing species mixing in the microchannel. Consequently, the use of an AC electric field together with patchwise surface heterogeneities permits a significant reduction in both the mixing channel length and the retention time required to attain a homogeneous solution.

Method and apparatus for determining minority carrier diffusion length in semiconductors

DOEpatents

Moore, Arnold R.

1984-01-01

Method and apparatus are provided for determining the diffusion length of minority carriers in semiconductor material, particularly amorphous silicon which has a significantly small minority carrier diffusion length using the constant magnitude surface-photovoltage (SPV) method. Steady or modulated illumination at several wavelengths provides the light excitation on the surface of the material to generate the SPV. A manually controlled or automatic servo system maintains a constant predetermined value of the SPV for each wavelength. A drop of a transparent electrolyte solution containing redox couples (preferably quinhydrone) having an oxidation-reduction potential (E) in the order of +0.6 to -1.65 volts couples the SPV to a measurement system. The drop of redox couple solution functions to create a liquid Schottky barrier at the surface of the material. Illumination light is passed through a transparent rod supported over the surface and through the drop of transparent electrolyte. The drop is held in the gap between the rod and the surface. Steady red light is also used as an optical bias to reduce deleterious space-charge effects that occur in amorphous silicon.

Coarse-grained modeling of proline rich protein 1 (PRP-1) in bulk solution and adsorbed to a negatively charged surface.

PubMed

Skepö, Marie; Linse, Per; Arnebrant, Thomas

2006-06-22

Structural properties of the acidic proline rich protein PRP-1 of salivary origin in bulk solution and adsorbed onto a negatively charged surface have been studied by Monte Carlo simulations. A simple model system with focus on electrostatic interactions and short-ranged attractions among the uncharged amino acids has been used. In addition to PRP-1, some mutants were considered to assess the role of the interactions in the systems. Contrary to polyelectrolytes, the protein has a compact structure in salt-free bulk solutions, whereas at high salt concentration the protein becomes more extended. The protein adsorbs to a negatively charged surface, although its net charge is negative. The adsorbed protein displays an extended structure, which becomes more compact upon addition of salt. Hence, the conformational response upon salt addition in the adsorbed state is the opposite as compared to that in bulk solution. The conformational behavior of PRP-1 in bulk solution and at charged surfaces as well as its propensity to adsorb to surfaces with the same net charge are rationalized by the block polyampholytic character of the protein. The presence of a triad of positively charged amino acids in the C-terminal was found to be important for the adsorption of the protein.

Cellulose nanocrystals with tunable surface charge for nanomedicine

NASA Astrophysics Data System (ADS)

Hosseinidoust, Zeinab; Alam, Md Nur; Sim, Goeun; Tufenkji, Nathalie; van de Ven, Theo G. M.

2015-10-01

Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge.Crystalline nanoparticles of cellulose exhibit attractive properties as nanoscale carriers for bioactive molecules in nanobiotechnology and nanomedicine. For applications in imaging and drug delivery, surface charge is one of the most important factors affecting the performance of nanocarriers. However, current methods of preparation offer little flexibility for controlling the surface charge of cellulose nanocrystals, leading to compromised colloidal stability under physiological conditions. We report a synthesis method that results in nanocrystals with remarkably high carboxyl content (6.6 mmol g-1) and offers continuous control over surface charge without any adjustment to the reaction conditions. Six fractions of nanocrystals with various surface carboxyl contents were synthesized from a single sample of softwood pulp with carboxyl contents varying from 6.6 to 1.7 mmol g-1 and were fully characterized. The proposed method resulted in highly stable colloidal nanocrystals that did not aggregate when exposed to high salt concentrations or serum-containing media. Interactions of these fractions with four different tissue cell lines were investigated over a wide range of concentrations (50-300 μg mL-1). Darkfield hyperspectral imaging and confocal microscopy confirmed the uptake of nanocrystals by selected cell lines without any evidence of membrane damage or change in cell density; however a charge-dependent decrease in mitochondrial activity was observed for charge contents higher than 3.9 mmol g-1. A high surface carboxyl content allowed for facile conjugation of fluorophores to the nanocrystals without compromising colloidal stability. The cellular uptake of fluoresceinamine-conjugated nanocrystals exhibited a time-dose dependent relationship and increased significantly with doubling of the surface charge. Electronic supplementary information (ESI) available: Additional results are presented in the ESI in Fig. S1 through S4. See DOI: 10.1039/c5nr02506k

Modelling CEC variations versus structural iron reduction levels in dioctahedral smectites. Existing approaches, new data and model refinements.

PubMed

Hadi, Jebril; Tournassat, Christophe; Ignatiadis, Ioannis; Greneche, Jean Marc; Charlet, Laurent

2013-10-01

A model was developed to describe how the 2:1 layer excess negative charge induced by the reduction of Fe(III) to Fe(II) by sodium dithionite buffered with citrate-bicarbonate is balanced and applied to nontronites. This model is based on new experimental data and extends structural interpretation introduced by a former model [36-38]. The 2:1 layer negative charge increase due to Fe(III) to Fe(II) reduction is balanced by an excess adsorption of cations in the clay interlayers and a specific sorption of H(+) from solution. Prevalence of one compensating mechanism over the other is related to the growing lattice distortion induced by structural Fe(III) reduction. At low reduction levels, cation adsorption dominates and some of the incorporated protons react with structural OH groups, leading to a dehydroxylation of the structure. Starting from a moderate reduction level, other structural changes occur, leading to a reorganisation of the octahedral and tetrahedral lattice: migration or release of cations, intense dehydroxylation and bonding of protons to undersaturated oxygen atoms. Experimental data highlight some particular properties of ferruginous smectites regarding chemical reduction. Contrary to previous assumptions, the negative layer charge of nontronites does not only increase towards a plateau value upon reduction. A peak is observed in the reduction domain. After this peak, the negative layer charge decreases upon extended reduction (>30%). The decrease is so dramatic that the layer charge of highly reduced nontronites can fall below that of its fully oxidised counterpart. Furthermore, the presence of a large amount of tetrahedral Fe seems to promote intense clay structural changes and Fe reducibility. Our newly acquired data clearly show that models currently available in the literature cannot be applied to the whole reduction range of clay structural Fe. Moreover, changes in the model normalising procedure clearly demonstrate that the investigated low tetrahedral bearing nontronites (SWa-1, GAN and NAu-1) all exhibit the same behaviour at low reduction levels. Consequently, we restricted our model to the case of moderate reduction (<30%) in low tetrahedral Fe-bearing nontronites. Our adapted model provides the relative amounts of Na(+) (p) and H(+) (ni) cations incorporated in the structure as a function of the amount of Fe reduction. Two equations enable the investigated systems to be described: p=m/(1+Kr·ω·mrel) and ni=Kr·ω·m·mrel/(1+Kr·ω·mrel); where m is the Fe(II) content, mrel, the reduction level (m/mtot), ω, the cation exchange capacity (CEC, and Kr, an empirical constant specific to the system. Copyright © 2013 Elsevier Inc. All rights reserved.

Surface correlation effects in two-band strongly correlated slabs.

PubMed

Esfahani, D Nasr; Covaci, L; Peeters, F M

2014-02-19

Using an extension of the Gutzwiller approximation for an inhomogeneous system, we study the two-band Hubbard model with unequal band widths for a slab geometry. The aim is to investigate the mutual effect of individual bands on the spatial distribution of quasi-particle weight and charge density, especially near the surface of the slab. The main effect of the difference in band width is the presence of two different length scales corresponding to the quasi-particle profile of each band. This is enhanced in the vicinity of the critical interaction of the narrow band where an orbitally selective Mott transition occurs and a surface dead layer forms for the narrow band. For the doped case, two different regimes of charge transfer between the surface and the bulk of the slab are revealed. The charge transfer from surface/center to center/surface depends on both the doping level and the average relative charge accumulated in each band. Such effects could also be of importance when describing the accumulation of charges at the interface between structures made of multi-band strongly correlated materials.

Surface Charge and Hydrophobicity of Endospores of Bacillus anthracis and Related Species in Aqueous Solution

EPA Science Inventory

The surface properties of microorganisms play an important role in attachment and detachment in the environment. The change in surface charge can effect coagulation, disinfection, adhesion to surfaces, uptake of chemicals, and environmental transport. In aqueous solution, cell s...

Convective transport of electric charge within the planetary boundary layer

NASA Astrophysics Data System (ADS)

Nicoll, Keri; Harrison, Giles; Silva, Hugo; Silgado, Rui; Melgao, Marta

2017-04-01

Turbulent and convective processes within the planetary boundary layer are responsible for the transport of moisture, momentum and particulate matter, but are also of major importance in determining the electrical charge structure of the lower atmosphere. This paper presents rare experimental measurements of vertical profiles of charge measured during fair weather conditions by specially instrumented radiosonde balloons over Alqueva, Portugal during the summer of 2014. Space charge was measured directly using a sensitive electrometer, rather than the conventional method of deriving it from electric field measurements. The high frequency of balloon flights enabled the diurnal variation in the vertical profile of charge within the boundary layer to be examined in detail, with much smaller levels of charge (up to 20pC m-3) observed during stable night time periods than during the day. Following sunrise, the evolution of the charge profile was much more complex, showing a dependence on lofting of surface aerosol due to daytime convection. This produced charge up to 92pC m-3 up to 500m above the surface. The diurnal variation in the integrated column of charge above the measurement site was also found to track closely with the diurnal variation in near surface charge as measured by an electric field mill at the same site, confirming the importance of the link between surface charge generation processes and aloft. Co-located lidar backscatter measurements were also made during the measurement campaign and will be discussed here in the context of the effect of aerosol on the vertical charge profile.

Piezoelectric modulation of surface voltage in GaN and AlGaN/GaN: charge screening effects and 2DEG

NASA Astrophysics Data System (ADS)

Wilson, Marshall; Schrayer, Bret; Savtchouk, Alexandre; Hillard, Bob; Lagowski, Jacek

2017-02-01

Surface voltage response to pulses of piezoelectric polarization is measured with a Kelvin-probe providing a unique means for investigation of the dynamics of polarization induced sheet charge and 2DEG. Combined with biasing of the surface with a corona-deposited charge from accumulation to deep depletion and corresponding non-contact C-V type characterization, the technique identifies surface band bending and interface traps as key factors that affect the magnitude and time decay of piezoelectric polarization. For 2DEG structures, surface potential pinning is observed when the 2DEG is fully populated. Pinning is released by negative corona charging to fully deplete the 2DEG. These results are consistent with the role of surface states. Presently demonstrated polarization modulation and wafer scale measurements shall impact the in-depth characterization and fundamental understanding of AlGaN/GaN 2DEG structures.

Fibrinogen adsorption onto 316L stainless steel under polarized conditions.

PubMed

Gettens, Robert T T; Gilbert, Jeremy L

2008-04-01

Adsorption of the plasma protein fibrinogen onto electrically polarized 316L stainless steel was observed and quantified using both in situ and ex situ atomic force microscopy (AFM) techniques. Significant differences in fibrinogen adsorption were observed across voltages. Ex situ studies showed significantly lower area coverage (theta) and height of adsorbed Fb on cathodically polarized surfaces when compared to anodically polarized surfaces. Conformational differences in the protein may explain the distinctions in Fb surface area coverage (theta) and height between the anodic and cathodic cases. In situ studies showed significantly slower kinetics of Fb adsorption onto surfaces below -100 mV (vs. Ag/AgCl) compared to surfaces polarized above -100 mV. Electrochemical current density data showed large charge transfer processes (approximately 1 x 10(-5) to 1 x 10(-4) A/cm(2)) taking place on the 316L SS surfaces at voltages below -100 mV (vs. Ag/AgCl). These relatively large current densities point to flux of ionic species away from the surface as a major source of the reduction in adsorption kinetics rather than just hydrophilic or electrostatic effects. Copyright 2007 Wiley Periodicals, Inc.

Studies of oxidation and thermal reduction of the Cu(100) surface using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2010-03-01

Changes in the surface of an oxidized Cu(100) single crystal resulting from vacuum annealing have been investigated using positron annihilation induced Auger electron spectroscopy (PAES). PAES measurements show a large increase in the intensity of the Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 C. The intensity then decreases monotonically as the annealing temperature is increased to ˜600 C. In contrast, the O KLL PAES intensity is the lowest at 300 C and it starts to increase again as the temperature is increased further. PAES results are analyzed by performing calculations of positron surface states and annihilation characteristics taking into account the charge redistribution at the surface, surface reconstructions, and changes of electronic properties of the surfaces with adsorbed oxygen. Possible explanation is proposed for the observed behavior of the intensity of positron annihilation induced Cu M2,3VV and O KLL Auger peaks and probabilities of annihilation of surface trapped positrons with Cu 3p and O 1s core-level electrons with changes of the annealing temperature.

Bounding Extreme Spacecraft Charging in the Lunar Environment

NASA Technical Reports Server (NTRS)

Minow, Joseph I.; Parker, Linda N.

2008-01-01

Robotic and manned spacecraft from the Apollo era demonstrated that the lunar surface in daylight will charge to positive potentials of a few tens of volts because the photoelectron current dominates the charging process. In contrast, potentials of the lunar surface in darkness which were predicted to be on the order of a hundred volts negative in the Apollo era have been shown more recently to reach values of a few hundred volts negative with extremes on the order of a few kilovolts. The recent measurements of night time lunar surface potentials are based on electron beams in the Lunar Prospector Electron Reflectometer data sets interpreted as evidence for secondary electrons generated on the lunar surface accelerated through a plasma sheath from a negatively charged lunar surface. The spacecraft potential was not evaluated in these observations and therefore represents a lower limit to the magnitude of the lunar negative surface potential. This paper will describe a method for obtaining bounds on the magnitude of lunar surface potentials from spacecraft measurements in low lunar orbit based on estimates of the spacecraft potential. We first use Nascap-2k surface charging analyses to evaluate potentials of spacecraft in low lunar orbit and then include the potential drops between the ambient space environment and the spacecraft to the potential drop between the lunar surface and the ambient space environment to estimate the lunar surface potential from the satellite measurements.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskin, Julia; Johnson, Grant E.; Prabhakaran, Venkateshkumar

Immobilization of complex molecules and clusters on supports plays an important role in a variety of disciplines including materials science, catalysis and biochemistry. In particular, deposition of clusters on surfaces has attracted considerable attention due to their non-scalable, highly size-dependent properties. The ability to precisely control the composition and morphology of clusters and small nanoparticles on surfaces is crucial for the development of next generation materials with rationally tailored properties. Soft- and reactive landing of ions onto solid or liquid surfaces introduces unprecedented selectivity into surface modification by completely eliminating the effect of solvent and sample contamination on the qualitymore » of the film. The ability to select the mass-to-charge ratio of the precursor ion, its kinetic energy and charge state along with precise control of the size, shape and position of the ion beam on the deposition target makes soft-landing an attractive approach for surface modification. High-purity uniform thin films on surfaces generated using mass-selected ion deposition facilitate understanding of critical interfacial phenomena relevant to catalysis, energy generation and storage, and materials science. Our efforts have been directed toward understanding charge retention by soft-landed metal and metal-oxide cluster ions, which may affect both their structure and reactivity. Specifically, we have examined the effect of the surface on charge retention by both positively and negatively charged cluster ions. We found that the electronic properties of the surface play an important role in charge retention by cluster cations. Meanwhile, the electron binding energy is a key factor determining charge retention by cluster anions. These findings provide the scientific foundation for the rational design of interfaces for advanced catalysts and energy storage devices. Further optimization of electrode-electrolyte interfaces for applications in energy storage and electrocatalysis may be achieved by understanding and controlling the properties of soft-landed cluster ions.« less

Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

PubMed

Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

2015-05-20

A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces.

Study of space charge layer in silver bromide microcrystals by means of ultraviolet photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Tani, Tadaaki; Inami, Yoshiyasu

2000-09-01

Ultraviolet photoelectron spectroscopy has been successfully used to measure the heights of the tops of the valence bands of the surfaces of AgBr layers on Ag substrates for the verification of the space charge layer model. According to this model, the positive space charge layer (composed of negative charges with excess negative kink sites on the surface and corresponding positive charges with interstitial silver ions in the interior) is formed in silver halides, causing the difference in the electronic energy levels between their surface and interior. The depression of the positive space charge layer of AgBr caused by such adsorbates as photographic stabilizers and antifoggants was estimated from the decrease in the ionic conductivity of cubic AgBr microcrystals by the adsorbates. It was confirmed by the decrease in the heights of the tops of the valence bands of the surfaces of AgBr layers caused by the adsorbates in the presence of thin gelatin membranes on their surfaces. This result provided the explanation for the fact that the adsorbates increased the number of the microcrystals which formed latent image centers on the surface and decreased the number of the microcrystals, which formed latent image centers in the interior.

Instrumentation and Methodology Development for Mars Mission

NASA Technical Reports Server (NTRS)

Chen, Yuan-Liang Albert

2002-01-01

The Mars environment comprises a dry, cold and low air pressure atmosphere with low gravity (0.38g) and high resistivity soil. The global dust storms that cover a large portion of Mars were observed often from Earth. This environment provides an idea condition for triboelectric charging. The extremely dry conditions on the Martian surface have raised concerns that electrostatic charge buildup will not be dissipated easily. If triboelectrically generated charge cannot be dissipated or avoided, then dust will accumulate on charged surfaces and electrostatic discharge may cause hazards for future exploration missions. The low surface temperature on Mars helps to prolong the charge decay on the dust particles and soil. To better understand the physics of Martian charged dust particles is essential to future Mars missions. We research and design two sensors, velocity/charge sensor and PZT momentum sensors, to detect the velocity distribution, charge distribution and mass distribution of Martian charged dust particles. These sensors are fabricated at NASA Kenney Space Center, Electromagnetic Physics Testbed. The sensors will be tested and calibrated for simulated Mars atmosphere condition with JSC MARS-1 Martian Regolith simulant in this NASA laboratory.

The role of electrostatic interactions in protease surface diffusion and the consequence for interfacial biocatalysis.

PubMed

Feller, Bob E; Kellis, James T; Cascão-Pereira, Luis G; Robertson, Channing R; Frank, Curtis W

2010-12-21

This study examines the influence of electrostatic interactions on enzyme surface diffusion and the contribution of diffusion to interfacial biocatalysis. Surface diffusion, adsorption, and reaction were investigated on an immobilized bovine serum albumin (BSA) multilayer substrate over a range of solution ionic strength values. Interfacial charge of the enzyme and substrate surface was maintained by performing the measurements at a fixed pH; therefore, electrostatic interactions were manipulated by changing the ionic strength. The interfacial processes were investigated using a combination of techniques: fluorescence recovery after photobleaching, surface plasmon resonance, and surface plasmon fluorescence spectroscopy. We used an enzyme charge ladder with a net charge ranging from -2 to +4 with respect to the parent to systematically probe the contribution of electrostatics in interfacial enzyme biocatalysis on a charged substrate. The correlation between reaction rate and adsorption was determined for each charge variant within the ladder, each of which displayed a maximum rate at an intermediate surface concentration. Both the maximum reaction rate and adsorption value at which this maximum rate occurs increased in magnitude for the more positive variants. In addition, the specific enzyme activity increased as the level of adsorption decreased, and for the lowest adsorption values, the specific enzyme activity was enhanced compared to the trend at higher surface concentrations. At a fixed level of adsorption, the specific enzyme activity increased with positive enzyme charge; however, this effect offers diminishing returns as the enzyme becomes more highly charged. We examined the effect of electrostatic interactions on surface diffusion. As the binding affinity was reduced by increasing the solution ionic strength, thus weakening electrostatic interaction, the rate of surface diffusion increased considerably. The enhancement in specific activity achieved at the lowest adsorption values is explained by the substantial rise in surface diffusion at high ionic strength due to decreased interactions with the surface. Overall, knowledge of the electrostatic interactions can be used to control surface parameters such as surface concentration and surface diffusion, which intimately correlate with surface biocatalysis. We propose that the maximum reaction rate results from a balance between adsorption and surface diffusion. The above finding suggests enzyme engineering and process design strategies for improving interfacial biocatalysis in industrial, pharmaceutical, and food applications.

Silver nanoparticles as a key feature of a plasma polymer composite layer in mitigation of charge injection into polyethylene under dc stress

NASA Astrophysics Data System (ADS)

Milliere, L.; Maskasheva, K.; Laurent, C.; Despax, B.; Boudou, L.; Teyssedre, G.

2016-01-01

The aim of this work is to limit charge injection from a semi-conducting electrode into low density polyethylene (LDPE) under dc field by tailoring the polymer surface using a silver nanoparticles-containing layer. The layer is composed of a plane of silver nanoparticles embedded in a semi-insulating organosilicon matrix deposited on the polyethylene surface by a plasma process. Size, density and surface coverage of the nanoparticles are controlled through the plasma process. Space charge distribution in 300 μm thick LDPE samples is measured by the pulsed-electroacoustic technique following a short term (step-wise voltage increase up to 50 kV mm-1, 20 min in duration each, followed by a polarity inversion) and a longer term (up to 12 h under 40 kV mm-1) protocols for voltage application. A comparative study of space charge distribution between a reference polyethylene sample and the tailored samples is presented. It is shown that the barrier effect depends on the size distribution and the surface area covered by the nanoparticles: 15 nm (average size) silver nanoparticles with a high surface density but still not percolating form an efficient barrier layer that suppress charge injection. It is worthy to note that charge injection is detected for samples tailored with (i) percolating nanoparticles embedded in organosilicon layer; (ii) with organosilicon layer only, without nanoparticles and (iii) with smaller size silver particles (<10 nm) embedded in organosilicon layer. The amount of injected charges in the tailored samples increases gradually in the samples ranking given above. The mechanism of charge injection mitigation is discussed on the basis of complementary experiments carried out on the nanocomposite layer such as surface potential measurements. The ability of silver clusters to stabilize electrical charges close to the electrode thereby counterbalancing the applied field appears to be a key factor in explaining the charge injection mitigation effect.

The Thomas-Fermi model in the theory of systems of charged particles above the surface of liquid dielectrics

NASA Astrophysics Data System (ADS)

Lytvtnenko, D. M.; Slyusarenko, Yu. V.; Kirdin, A. I.

2012-10-01

A consistent theory of equilibrium states of same sign charges above the surface of liquid dielectric film located on solid substrate in the presence of external attracting constant electric field is proposed. The approach to the development of the theory is based on the Thomas-Fermi model generalized to the systems under consideration and on the variational principle. The using of self-consistent field model allows formulating a theory containing no adjustable constants. In the framework of the variational principle we obtain the self-consistency equations for the parameters describing the system: the distribution function of charges above the liquid dielectric surface, the electrostatic field potentials in all regions of the system and the surface profile of the liquid dielectric. The self-consistency equations are used to describe the phase transition associated with the formation of spatially periodic structures in the system of charges on liquid dielectric surface. Assuming the non-degeneracy of the gas of charges above the surface of liquid dielectric film the solutions of the self-consistency equations near the critical point are obtained. In the case of the symmetric phase we obtain the expressions for the potentials and electric fields in all regions of the studied system. The distribution of the charges above the surface of liquid dielectric film for the symmetric phase is derived. The system parameters of the phase transition to nonsymmetric phase - the states with a spatially periodic ordering are obtained. We derive the expression determining the period of two-dimensional lattice as a function of physical parameters of the problem - the temperature, the external attractive electric field, the number of electrons per unit of the flat surface area of the liquid dielectric, the density of the dielectric, its surface tension and permittivity, and the permittivity of the solid substrate. The possibility of generalizing the developed theory in the case of degenerate gas of like-charged particles above the liquid dielectric surface is discussed.

Surface functionalization of dopamine coated iron oxide nanoparticles for various surface functionalities

NASA Astrophysics Data System (ADS)

Sherwood, Jennifer; Xu, Yaolin; Lovas, Kira; Qin, Ying; Bao, Yuping

2017-04-01

We present effective conjugation of four small molecules (glutathione, cysteine, lysine, and Tris(hydroxymethyl)aminomethane) onto dopamine-coated iron oxide nanoparticles. Conjugation of these molecules could improve the surface functionality of nanoparticles for more neutral surface charge at physiological pH and potentially reduce non-specific adsorption of proteins to nanoparticles surfaces. The success of conjugation was evaluated with dynamic light scattering by measuring the surface charge changes and Fourier transform infrared spectroscopy for surface chemistry analysis. The stability of dopamine-coated nanoparticles and the ability of conjugated nanoparticles to reduce the formation of protein corona were evaluated by measuring the size and charge of the nanoparticles in biological medium. This facile conjugation method opens up possibilities for attaching various surface functionalities onto iron oxide nanoparticle surfaces for biomedical applications.

Enhanced flashover strength in polyethylene nanodielectrics by secondary electron emission modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Weiwang; Li, Shengtao, E-mail: sli@xjtu.edu.cn; Min, Daomin

2016-04-15

This work studies the correlation between secondary electron emission (SEE) characteristics and impulse surface flashover in polyethylene nanodielectrics both theoretically and experimentally, and illustrates the enhancement of flashover voltage in low-density polyethylene (LDPE) through incorporating Al{sub 2}O{sub 3} nanoparticles. SEE characteristics play key roles in surface charging and gas desorption during surface flashover. This work demonstrates that the presence of Al{sub 2}O{sub 3} nanoparticles decreases the SEE coefficient of LDPE and enhances the impact energy at the equilibrium state of surface charging. These changes can be explained by the increase of surface roughness and of surface ionization energy, and themore » strong interaction between nanoparticles and the polymer dielectric matrix. The surface charge and flashover voltage are calculated according to the secondary electron emission avalanche (SEEA) model, which reveals that the positive surface charges are reduced near the cathode triple point, while the presence of more nanoparticles in high loading samples enhances the gas desorption. Consequently, the surface flashover performance of LDPE/Al{sub 2}O{sub 3} nanodielectrics is improved.« less

In situ measurement of surface potential developed on MgO thin film surface under ion irradiation using ion scattering spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagatomi, T.; Kuwayama, T.; Takai, Y.

2009-11-15

The application of ion scattering spectroscopy (ISS) to the in situ measurement of the surface potential developed on an insulator surface under positive ion irradiation was investigated. The ISS spectra measured for a MgO film of 600 nm thickness on a Si substrate by the irradiation of 950 eV He{sup +} ions revealed that the surface is positively charged by approximately 180 V. For accurate measurement of the surface potential, a correction to take into account the angular deflection of primary ions induced by the high surface potential is required. The dependence of the surface potential on the sample temperaturemore » revealed that no charging is induced above 700 deg. C, indicating that accumulated charges can be removed by heating to 700 deg. C. From the measurement of the ion-induced secondary electron yield using a collector electrode located in front of the sample surface, the surface potential and ion-induced secondary electron yield were found to be strongly affected by the experimental setup. Secondary electrons produced by the impact of slow positive secondary ions, the maximum energy of which corresponds to the surface potential, play an important role when the bias voltage applied to the collector electrode is positively high for the present experimental setup. The surface potential developed on the surface of MgO films of 600 and 200 nm thickness was measured in situ, revealing that the amount of accumulated charges and the time required to attain the steady state of charging are slightly dependent on the beam current of primary ions and strongly dependent on the thickness of the MgO film. The present results confirmed that the application of ISS has high potential for investigating charging phenomena and the secondary electron emission from insulator surfaces under positive ion irradiation.« less

Ferrocene Containing Copolymers with Improved Electrostatic Dissipation Properties for Advanced Applications

NASA Technical Reports Server (NTRS)

Smith, T. M.; Nelson, G. L.

2005-01-01

Electrostatic dissipative polymers are used for a variety of functions. Typical methods utilized to transform electrically insulating polymers into either charge dissipative or conductive materials involve incorporating a conductive filler, conductive polymer, oxidizing the surface using plasma, or incorporating surfactants that act as surface wetting agents. Another approach is to synthesize a block copolymer that is expected to result in better electrical properties with minimal impacts to physical, fire, and thermal properties. One such block that can be added into the main chain of polymers is a diol terminated ferrocene oligomer, which is expected to impart electrostatic dissipative properties into the host polymer while concurrently improving the overall fire properties. Previous work with polyurethanes incorporating a ferrocene oligomer into the main chain resulted in much improved fire retardancy. In dealing with electrostatic dissipative materials the important questions are: how easily does the material charge and how quickly can the charge move to ground. One normally describes the materials conductivity, but conductivity only measures the fastest path for an electron not the slowest path. The slowest path is the one of interest, since it is left on the surface and thus can cause discharges. In order to assess ease of charging and decay times corona charge dissipation measurements can accurately assess these properties by introducing a charge on the surface of the material then measuring the surface voltage and the amount of charge deposited. The charge decay curve then will give an indication of a materials electrostatic dissipation properties. Normally, triboelectric testing can be performed, but results vary. Corona charge dissipation results are more repeatable.

Self-consistent simulation of radio frequency multipactor on micro-grooved dielectric surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Libing; Wang, Jianguo, E-mail: wanguiuc@mail.xjtu.edu.cn; Northwest Institute of Nuclear Technology, Xi'an, Shaanxi 710024

2015-02-07

The multipactor plays a key role in the surface breakdown on the feed dielectric window irradiated by high power microwave. To study the suppression of multipactor, a 2D electrostatic PIC-MCC simulation code was developed. The space charge field, including surface deposited charge and multipactor electron charge field, is obtained by solving 2D Poisson's equation in time. Therefore, the simulation is self-consistent and does not require presetting a fixed space charge field. By using this code, the self-consistent simulation of the RF multipactor on the periodic micro-grooved dielectric surface is realized. The 2D space distributions of the multipactor electrons and spacemore » charge field are presented. From the simulation results, it can be found that only half slopes have multipactor discharge when the slope angle exceeds a certain value, and the groove presents a pronounced suppression effect on the multipactor.« less

Hydrolysis-controlled protein adsorption and antifouling behaviors of mixed charged self-assembled monolayer: A molecular simulation study.

PubMed

Liu, Jie; Zhou, Jian

2016-08-01

Understanding the mechanism of the antimicrobial and antifouling properties of mixed charged materials is of great significance. The interactions between human gamma fibrinogen (γFg) and mixed carboxylic methyl ether-terminated (COOCH3-) and trimethylamino-terminated (N(CH3)3(+)-) SAMs and the influence of hydrolysis were studied by molecular simulations. After hydrolysis, the mixed SAMs exhibit behaviors from antimicrobial to antifouling, since the COOCH3-thiols were translated into carboxylic acid (COO(-)-) terminated thiols, which carried a net charge of -1 e. Simulation results showed that the main differences between COOCH3-/N(CH3)3(+)-SAM and COO(-)-/N(CH3)3(+)-SAM are the charged property and the hydration layer above the surface. γFg could stably adsorb on the positively-charged COOCH3-/N(CH3)3(+)-SAM. The adsorption behavior is mainly induced by the strong electrostatic attraction. There is a single hydration layer bound to the surface, which is related to the N(CH3)3(+) groups. The van der Waals repulsion between γFg and the single hydration layer are not strong enough to compensate the strong electrostatic attraction. After hydrolysis, the positively-charged SAM was transferred to a neutral mixed charged surface, the electrostatic attraction between γFg and the surface disappears. Meanwhile, the SAM surface is covered by double hydration layers, which is induced by the N(CH3)3(+) and COO(-) groups; water molecules around COO(-) groups are obviously denser than that around N(CH3)3(+) groups. With the combined contribution from double hydration layers and the vanishment of electrostatic attraction, γFg is forced to desorb from the surface. After hydrolysis, the internal structure of mixed SAM appears more ordered due to the electrostatic interactions between charged groups on the top of SAMs. The antimicrobial and antifouling materials are of great importance in many biological applications. The strong hydration property of surfaces and the interactions between proteins and surfaces play a key role in resisting protein adsorption. The mixed SAMs, constructed from a 1:1 combination of COOCH3- and N(CH3)3(+)-terminated thiols, can induce protein adsorption mainly through the electrostatic interaction. When the COOCH3-terminated thiols were hydrolyzed to negatively charged COO(-)-terminated thiols, the mixed-charged SAMs switched from antimicrobial to antifouling. Due to the strong hydration property of the mixed charged SAMs, the adsorbed γFg moved away from the surface. Understanding the interactions between protein and mixed-charged SAMs in the atomistic level is important for the practical design and development of new antimicrobial and antifouling materials. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Hollow SnO2 nanospheres with oxygen vacancies entrapped by a N-doped graphene network as robust anode materials for lithium-ion batteries.

PubMed

Wu, Naiteng; Du, Wuzhou; Gao, Xu; Zhao, Liang; Liu, Guilong; Liu, Xianming; Wu, Hao; He, Yan-Bing

2018-06-21

The practical application of tin dioxide (SnO2) in lithium-ion batteries has been greatly hindered by its large volumetric expansion and low conductivity. Thus, a rational design of the size, geometry and the pore structure of SnO2-based nanomaterials is still a dire demand. To this end, herein we report an effective approach for engineering hollow-structured SnO2 nanospheres with adequate surface oxygen vacancies simultaneously wrapped by a nitrogen-doped graphene network (SnO2-x/N-rGO) through an electrostatic adsorption-induced self-assembly together with a thermal reduction process. The close electrostatic attraction achieved a tight and uniform combination of positively charged SnO2 nanospheres with negatively charged graphene oxide (GO), which can alleviate the aggregation and volume expansion of the entrapped SnO2 nanospheres. Subsequent thermal treatment not only ensures a significant reduction of the GO sheets accompanying nitrogen-doping, but also induces the generation of oxygen vacancies on the surface of the SnO2 hollow nanospheres, together building up a long-range and bicontinuous transfer channel for rapid electron and ion transport. Because of these structural merits, the as-built SnO2-x/N-rGO composite used as the anode material exhibits excellent robust cycling stability (∼912 mA h g-1 after 500 cycles at 0.5 A g-1 and 652 mA h g-1 after 200 cycles at 1 A g-1) and superior rate capability (309 mA h g-1 at 10 A g-1). This facile fabrication strategy may pave the way for the construction of high performance SnO2-based anode materials for potential application in advanced lithium-ion batteries.